USOO6555634B1 (12) United States Patent (10) Patent No.: US 6,555,634 B1 Klosin et al. (45) Date of Patent: Apr. 29, 2003

(54) DI- AND TRI-HETEROATOM SUBSTITUTED 5,132,380 A 7/1992 Stevens et al...... 526/126 INDENYL METAL COMPLEXES 5,304,614 A 4/1994 Winter et al...... 526/127 5,321,106 A 6/1994 LaPointe ...... 526/126 (75) Inventors: Jerzy Klosin, Midland, MI (US); SE A 3.E. State st al ------5. WillianO O J. KuperJr., Sanford, MI 5,470,9932- . . . A 11/1995 DevoreOSCI C etal. al...... 556/11 (US); Peter N. Nickias, Midland, MI 5621,1262Y-4-2 A 4/1997 Canich et al...... 556/9 (US); Jasson T. Patton, Midland, MI 5,703,187. A 12/1997 Timmers ...... 526/282 (US) 5,721,185 A 2/1998 LaPointe et al...... 502/117 6,015,868 A 1/2000 Nickias et al...... 526/127 (73) Assignee: The Dow Chemical Company, 6,268,444 B1 7/2001 Klosin et al...... 526/127 Midland, MI (US(US) FOREIGN PATENT DOCUMENTS (*) Notice: Subject to any disclaimer, the term of this EP 416815 3/1991 patent is extended or adjusted under 35 EP 51.4828 11/1992 U.S.C. 154(b) by 0 days. EP 582195 2/1994 EP 577581 11/1994 (21) Appl. No.: 09/936,018 WO WO95/07942 3/1995 1.-1. WO WO 96/13.529 5/1996 (22) PCT Filed: Mar. 17, 2000 WO WO 98/06727 2/1998 (86) PCT No.: PCT/US00/07372 WO WO 98/06728 2/1998 WO WOOO/69870 A1 * 11/2000 ...... CO8F/17/OO S371 (c)(1), (2), (4) Date: Sep. 7, 2001 OTHER PUBLICATIONS (87) PCT Pub. No.: WO00/69871 J. Organometallic Chem. 1996, 520, 63-68 E. Barsties, S. Schaible, M. H. Prosenc, u. Rief, W. Roll, O. Weyland, B. PCT Pub. Date: Nov. 23, 2000 Dorerer, and H. H. Brintzinger. O O J. Organometallic Chem. 1996, 519, 269-272, H. Plenio, Related U.S. Application Data and D. Birth. (60) Provisional application No. 60/133,994, filed on May 13, 1999. * cited by examiner (51) Int. Cl."7 ...... C08F 4/64 Primary Examiner-David W. Wu (52) U.S. Cl...... 526/161; 526/160; 526/170; Assistant Examiner Rip A. Lee 526/172; 556/11; 556/51; 556/52; 502/103 (58) Field of Search ...... 526/161,172, (57) ABSTRACT 526/160, 170, 126; 556/51, 52, 11; 502/103 Novel metal complexes containing at least two heteroatoms attached to an indenyl or Substituted indenyl radical which (56) References Cited is bridged by ligand group thereby forming a covalent or U.S. PATENT DOCUMENTS coordinate/covalent bond to the metal, the use of Such metal complexes in the formation of polymerization catalysts and 5,055.438 A 10/1991 Canich ...... 502/117 rocesses for polvmerizing C-olefins using Such catalvsts 5,057.475 A 10/1991 Canich et al...... 502/104 P poly 9. 9. ySLS. 5,064,802 A 11/1991 Stevens et al...... 502/155 5,096,867 A 3/1992 Canich ...... 502/103 8 Claims, No Drawings US 6,555,634 B1 1 D- AND TR-HETEROATOM SUBSTITUTED I INDENYL METAL COMPLEXES RA RA This application claims the benefit of Provisional Appli RA cation No. 60/133,994 filed May 13, 1999. RA FIELD OF THE INVENTION RA

This invention relates to a class of metal complexes, the 1O RA / ligands used to prepare these metal complexes and to olefin polymerization catalysts derived therefrom that are particu larly Suitable for use in a polymerization proceSS for pre where M is a metal from one of Groups 3 to 13 of the paring polymers by polymerization of C-olefins and mix Periodic Table of the Elements, the lanthanides or actinides, tures of C-olefins. 15 which is in the +2, +3 or +4 formal oxidation State, R independently each occurrence is hydrogen, R or BACKGROUND TR, with the proviso that in at least two but not more than three occurrences R is TR is Constrained geometry metal complexes and methods for j is 1 or 2, and when j is 1, T is oxygen or Sulfur and when j is 2, T is nitrogen or phosphorus, their preparation are disclosed in U.S. Pat. No. 5,703,187; R’ independently each occurrence is a group having from U.S. Pat. No. 5,321,106; U.S. Pat. No. 5,721,185; U.S. Pat. 1 to 80 atoms not counting hydrogen, which is No. 5,374,696; U.S. Pat. No. 5,055.438; U.S. Pat. No. hydrocarbyl, hydrocarbylsilyl, halo-substituted 5,057,475; U.S. Pat. No. 5,096,867; U.S. Pat. No. 5,064,802; hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, U.S. Pat. No. 5,132,380; U.S. Pat. No. 5,470,993, as well as 25 hydrocarby lamino-substituted hydrocarbyl, or EP-A-514.828, and elsewhere. hydrocarbylsilyl-substituted hydrocarbyl, or two R' groups are joined together forming a divalent ligand U.S. Pat. Nos. 5,350,817 and 5,304,614 disclose bridged grOup, Zirconocene complexes, wherein two indenyl groups are Z is a divalent moiety bound to the substituted indenyl covalently linked together by a bridge containing carbon or group and bound to M by either covalent or coordinate/ Silicon, which are useful for the polymerization of propy covalent bonds, comprising boron or a member of lene. Group 14 of the Periodic Table of the Elements, and EP-A-577,581 discloses unsymmetrical bis-Cp metal also comprising nitrogen, phosphorus, Sulfur or Oxy gen, locenes containing a fluorenyl ligand with heteroatom Sub 35 Stituents. X is an anionic or dianionic ligand group having up to 60 atoms (including ligands that are cyclic, delocalized, E. Barsties; S. Schaible; M.-H. Prosenc; U. Rief, W. Roll; JL-bound ligand groups); O. Weyland; B. Dorerer; H.-H. Brintzinger J. Organome X" independently each occurrence is a Lewis base ligand tallic Chem. 1996, 520, 63–68, and H. Plenio; D. Birth J. having up to 20 atoms, Organometallic Chem. 1996, 519, 269-272 disclose systems 40 p is a number from 0 to 5, (when each X is an anionic in which the cyclopentadienyl ring of the indenyl is Substi ligand, p is two less than the formal oxidation State of tuted with a dimethylamino group in non-bridged and M, when Some or all X groups are dianionic ligand Si-bridged bis-indenyl complexes useful for the formation of groups each dianionic X group accounts for two Valen isotactic polypropylene and polyethylene. 45 cies and p is correspondingly reduced in value); and Disclosure of random heteroatom Substitution in mono q is Zero, 1 or 2. Certain of the metal complexes wherein the metal is a Cp metallocenes is found in EP-A-416,815, WO95/07942, Group 3 or lanthanide metal are catalytically active for WO 96/13529, and U.S. Pat. No. 5,096,867 and U.S. Pat. polymerization of olefins without addition of an activator or No. 5,621,126. Specific heteroatom substitution of the 3 cocatalyst. Preferably however a cocatalyst is present. and 2-position of indenyl complexes of group 4 metals was 50 Accordingly, in one embodiment according to the present disclosed in WO98/06727 and WO/98/06728 respectively. invention, there is provided a catalyst composition for olefin The foregoing Specifically Substituted metal complexes have polymerization comprising: produced improved catalyst results, however, problems Still (A) a catalyst component comprising a metal complex as remain with catalyst efficiency and deactivation of the 55 previously defined; and catalyst under high temperature polymerization conditions. (B) a cocatalyst component comprising an activating It would be advantageous to be able to produce polyolefins cocatalyst wherein the molar ratio of (A) to (B) is from with higher molecular weights. It would also be advanta 1:10,000 to 100:1; or optionally catalyst component geous to be able to improve other physical characteristics of (A) is activated by use of an activating technique. the polymers produced by altering the Substitution around 60 Another embodiment of this invention is a catalyst com the cyclopentadienyl group of the metallocene complexes position for olefin polymerization comprising: used in olefin polymerization catalyst Systems. (A) a catalyst component comprising a metal complex as previously defined; and SUMMARY OF THE INVENTION (B) a cocatalyst component comprising an activating 65 cocatalyst wherein the molar ratio of (A) to (B) is from According to the present invention there are provided 1:10,000 to 100:1 wherein the metal complex is in the metal complexes corresponding to the formula: form of a radical cation. US 6,555,634 B1 3 4 Further according to the present invention there is pro herein refers to a copolymer of two or more olefins wherein Vided a process for the polymerization of olefins comprising higher molecular weight fractions of the polymer contain contacting one or more Co C-olefins under polymerization increased content of the higher molecular weight comono conditions with one of the aforementioned catalyst compo C. Olefins as used herein are Co aliphatic or aromatic Sitions. compounds containing vinylic unsaturation, as well as cyclic A preferred process of this invention is a high temperature compounds Such as cyclobutene, cyclopentene, and Solution polymerization process for the polymerization of norbornene, including norbornene Substituted in the 5- and olefins comprising contacting one or more Co C-olefins 6-positions with Co. hydrocarbyl groups. Also included under polymerization conditions with one of the aforemen are mixtures of Such olefins as well as mixtures of Such tioned catalyst compositions at a temperature from 100 C. olefins with Cao diolefin compounds. Examples of the to 250° C. latter compounds include ethylidene norbornene, 1,4- Within the scope of this invention are the polyolefin hexadiene, norbornadiene, and the like. The catalysts and products produced by the aforementioned processes. Pre processes herein are especially Suited for use in preparation ferred products have long chain branching and/or reverse of ethylene/1-butene, ethylene/1-hexene, ethylene/styrene, molecular architecture. 15 ethylene/propylene, ethylene/1-pentene, ethylene/4-methyl This invention also provides a cyclopentadienyl 1-pentene and ethylene/1-octene copolymers as well as containing ligand of one of the aforementioned metal com terpolymers of ethylene, propylene and a nonconjugated plexes where the ligand is in the form of: diene, such as, for example, EPDM terpolymers. Preferred coordination complexes according to the (A) a free acid with 2 protons capable of being deproto present invention are complexes corresponding to the for nated; mulas: (B) a dilithium, disodium or dipotassium salt; II (C) a magnesium salt: or (D) a mono or disilylated dianion. Within the scope of this aspect of the invention is the use 25 of one of these ligands for Synthesis to produce a metal complex of this invention, or, more specifically, the use of one of these ligands for Synthesis to produce a metal complex comprising a metal from one of Groups 3 to 13 of the Periodic Table of the Elements, the lanthanides or actinides, and from 1 to 4 of the ligands. The present catalysts and processes result in the highly III efficient production of high molecular weight olefin poly mers over a wide range of polymerization conditions, and especially at elevated temperatures. They are especially 35 useful for the solution or bulk polymerization of ethylene/ propylene (EP polymers), ethylene/octene (EO polymers), ethylene?styrene (ES polymers), propylene and ethylene/ propylene/diene (EPDM polymers) wherein the diene is ethylidenenorbornene, 1,4-hexadiene or Similar nonconju 40 gated diene. The use of elevated temperatures dramatically increases the productivity of Such processes due to the fact that increased polymer Solubility at elevated temperatures IV allows the use of increased conversions (higher concentra tion of polymer product) without exceeding Solution Viscos 45 ity limitations of the polymerization equipment. In addition, the use of higher polymerization temperatures results in a reduction of energy costs needed to devolatilize the reaction product. The catalysts of this invention may also be Supported on 50 a Support material and used in olefin polymerization pro ceSSes in a slurry or in the gas phase. The catalyst may be prepolymerized with one or more olefin monomers in Situ in a polymerization reactor or in a separate process with intermediate recovery of the prepolymerized catalyst prior to 55 the primary polymerization process. DETAILED DESCRIPTION All references to the Periodic Table of the Elements herein shall refer to the Periodic Table of the Elements, published 60 and copyrighted by CRC Press, Inc., 1989. Also, any refer ence to a Group or Groups shall be to the Group or Groups as reflected in this Periodic Table of the Elements using the IUPAC system for numbering groups. The full teachings of where T, R, j, M., Z, X, X", p and q are as previously defined, any patent, patent application, provisional application, or 65 and publication referred to herein are hereby incorporated by R’ independently is hydrogen or a group having from 1 reference. The term “reverse molecular architecture” as used to 80 atoms not counting hydrogen, which is US 6,555,634 B1 S 6 hydrocarbyl, hydrocarbylsilyl, halo-substituted -continued hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, VII hydrocarby lamino-substituted hydrocarbyl, or TRP, hydrocarbylsilyl-substituted hydrocarbyl, or two R' groups are joined together forming a divalent ligand RB' grOup. Preferred R and R groups are hydrogen and TRP, hydrocarbyl, hydrocarbylsilyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-Substituted hydrocarbyl and / Z. halogen Substituted hydrocarbyl groups having from 1 to 20 X'qXpM nonhydrogen atoms, more preferably hydrogen, alkyl, aryl VIII or aralkyl. TRP, More preferred R' groups are hydrogen, hydrocarbyl, hydrocarbylsilyl, hydrocarbyloxy-substituted hydrocarbyl, RB', O hydrocarbylamino-Substituted hydrocarbyl having from 1 to 15 TRP,B 20 nonhydrogen atoms, most preferably hydrogen, alkyl, aryl or aralkyl, or two R' groups together are an alkylene / Z. group having from 1 to 20 carbons. X'qXpM Preferred T groups are O or N, more preferably N. IX TRP, Preferred heteroatom-containing Substituents are at the 3, TRB. 5, or 6-position of the Substituted indenyl group and are J those wherein the TR group is methoxy, ethoxy, propoxy, RB' methylethyloxy, 1,1-dimethyethyloxy, trimethylsiloxy, 1,1- dimethylethyl(dimethylsilyl)oxy, dimethylamino, 25 TRP, diethylamino, methylethylamino, methylphenylamino, dipropylamino, dibutylamino, piperidino, morpholino, / Z. pyrrolidino, hexahydro-1H-azepin-1-yl, hexahydro-1(2H)- X'qXpM azocinyl, octahydro-1H-azonin-1-yl or octahydro-1(2H)- aZecinyl, or two adjacent TR, groups are -OCHO-. where Z, T, R, R, j, M, X, X", p and q are as previously More preferred are those wherein the TR group is defined with respect to formulas II, III IV and V. dimethylamino, methylphenylamino, piperidino or pyrroli Highly preferred are the metal complexes, the dino. heteroatom-containing ligands thereof, and metallated Preferred X groups are halide, alkyl, cycloalkyl, aryl, 35 derivatives thereof, where -Z - is -(Z-Y), with Z. aralkyl or cycloalkadienyl groups, said X having from 1 to bonded to Cp and Y bonded to M, and 20 atoms other than hydrogen. Y is -O-, -S-, -NR*-, -NR*, Preferred X' groups are carbon monoxide, phosphines, -OR*, or -SR*; especially trimethylphosphine, triethylphosphine, triph Z* is SiR*, CR*, SiR* SiR*, CR* CR*, CR*=CR*, enylphosphine and bis(1,2-dimethylphosphino)ethane; 40 CR* SiR* , CR* SiR* CR*, SiR* CR* SiR*, P(OR), wherein R is hydrocarbyl, silyl or a combination CR* CR* SiR*, CR* CR* CR*, or GeR*; and thereof; ethers, especially tetrahydrofuran, amines, espe R* independently each occurrence is hydrogen, or a cially pyridine, bipyridine, tetramethylethylenediamine member selected from hydrocarbyl, hydrocarbyloxy, (TMEDA), and triethylamine; olefins; and conjugated Sillyl, halogenated alkyl, halogenated aryl, and combi dienes having from 4 to 40 carbon atoms. Complexes 45 nations thereof, said R* having up to 20 nonhydrogen including the latter X" groups include those wherein the atoms, and optionally, two R* groups from Z, or an R* metal is in the +2 formal oxidation State. group from Z and an R* group from Y form a ring In another aspect of this invention either the ligand or System; metal complex has one or more fused rings or ring Systems when p is 2, q is Zero, M is in the +3 or +4 formal in addition to the Cp or indenyl wherein the one or more 50 Oxidation State, and X is independently each occurrence fused rings or ring Systems contain two or more ring chloride, methyl, benzyl, trimethylsilylmethyl, allyl, heteroatoms which are N, O, S, or P. Preferred ring heteroa cyclopentadienyl, pyrrolyl or two X groups together are toms are N or O, with N being more highly preferred. 1,4-butane-diyl, 2-butene-1,4-diy1, 2,3-dimethyl-2- The preferred complexes include ones corresponding to bute ne-1,4-diyl, 2-methyl-2-butene-1,4-diyl, or the formulas: 55 Xylanediyl. Also highly preferred are the metal complexes, the VI heteroatom-containing ligands thereof, and metallated derivatives thereof, where -Z- is -Z*-Y-, with Z. 60 bonded to Cp and Y bonded to M, and Y is -O-, -S-, -NR*-, or -PR*-, Z* is SiR*, CR*, SiR* SiR*, CR* CR*, CR*=CR*, CR* SiR* , CR* SiR* CR*, SiR* CR* SiR*, CR* CR* SiR*, CR* CR* CR*, or GeR*; and 65 R* independently each occurrence is hydrogen, or a member selected from hydrocarbyl, hydrocarbyloxy, Sillyl, halogenated alkyl, halogenated aryl, and combi US 6,555,634 B1 7 8 nations thereof, Said R* having up to 20 nonhydrogen -continued atoms, and optionally, two R* groups from Z, or an R* XIII group from Z and an R* group from Y form a ring TRP, System; TRP,B where p is 1, q is Zero, M is in the +2 or +3 formal RB' oxidation state, and X is 2-(N,N-dimethyl) TRB. aminobenzyl, 2-(N,N-dimethylaminomethyl)phenyl, J it. allyl, methallyl, trimethylsilylallyl, or cyclopentadi TXP-NRP enyl. Also highly preferred are the metal complexes, the wherein, TR, is dimethylamino, pyrrolidino, or methoxy, or heteroatom-containing ligands thereof, and metallated two adjacent TR, groups together are -OCH-O-, X derivatives thereof, where -Z-is-(Z-Y), with Z* independently each occurrence is chloride or methyl or two bonded to Cp and Y bonded to M, and X' groups collectively are a neutral 2,4-hexadiene or 1,4- 15 diphenyl-butadiene group, and R is t-butyl, isopropyl or Y is -O-, -S-, -NR*-, or -PR*-, cyclohexyl. Particularly preferred complexes are those of Z* is SiR*, CR*, SiR* SiR* , CR* CR*, CR*=CR*, the foregoing formulas X, XI, XII, and XIII, wherein R is CR* SiR* , CR* SiR* CR*, SiR* CR* SiR*, hydrogen or methyl, TR, is dimethylamino and pyrrolidino CR* CR* SiR*, CR* CR* CR*, or GeR*; and and X is halogen or methyl. The complexes can be prepared by use of well-known R* independently each occurrence is hydrogen, or a Synthetic techniques. Optionally a reducing agent can be member selected from hydrocarbyl, hydrocarbyloxy, employed to produce the lower oxidation State complexes. Sillyl, halogenated alkyl, halogenated aryl, and combi Such a process is disclosed in U.S. Pat. No. 5,470,993. The nations thereof, Said R* having up to 20 nonhydrogen reactions are conducted in a Suitable noninterfering Solvent atoms, and optionally, two R* groups from Z, or an R* 25 at a temperature from -100 to 300° C., preferably from -78 group from Z and an R* group from Y form a ring to 100° C., most preferably from 0 to 50° C. By the term System; “reducing agent herein is meant a metal or compound which, under reducing conditions, causes the metal M to be when p is 0, q is 1, M is in the +2 formal oxidation State, reduced from a higher to a lower oxidation State. Examples and X is 1,4-diphenyl-1,3-butadiene, 1,3-pentadiene or of Suitable metal reducing agents are alkali metals, alkaline 2,4-hexadiene. earth metals, aluminum and Zinc, alloys of alkali metals or A variety of metals can be used in the preparation of the alkaline earth metals. Such as Sodium/mercury amalgam and metal complexes of this invention. Desirably M is a metal Sodium/potassium alloy. Examples of Suitable reducing agent compounds are Sodium naphthalenide, potassium from one of Groups 3 to 13 of the Periodic Table of the graphite, lithium alkyls, lithium or potassium alkadienyls, Elements, the lanthanides or actinides, which is in the +2, +3 35 and Grignard reagents. Most preferred reducing agents are or +4 formal oxidation State, more desirably M is a metal the alkali metals or alkaline earth metals, especially lithium from one of Groups 3 to 13. Most preferred are those where or magnesium metal and n-butyllithium. M is a metal from Group 4. Titanium is the most highly Suitable reaction media for the formation of the com preferred metal. plexes include aliphatic and aromatic hydrocarbons, ethers, Further preferred coordination complexes of the invention 40 and cyclic ethers, particularly branched-chain hydrocarbons are complexes corresponding to the formulas: Such as isobutane, butane, pentane, hexane, heptane, octane, and mixtures thereof; cyclic and alicyclic hydrocarbons Such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; aromatic and 45 hydrocarbyl-Substituted aromatic compounds Such as benzene, toluene, and Xylene, C dialkyl ethers, C. dialkyl ether derivatives of (poly)alkylene glycols, and tet rahydrofuran. Mixtures of the foregoing are also Suitable. The Substituted inden-1-yl containing compounds may be 50 prepared by condensation of ketones with an amine or alcohol using Standard Synthetic techniques. Condensation XI with amines is well known from the teachings of W. E. Noland, V. Kameswaran J. Org. Chem. 1981, 46, 1940-1944, and elsewhere. An acid catalyst such as 55 p-toluene Sulfonic acid may be employed, and the water by-product is desirably azeotropically removed using a benzene or toluene Solvent under reflux conditions. A similar technique has been disclosed in O. Cervinka, The Chemistry of Enamines, Part 1, Ch. 9; Z. Rappoport, Ed., Wiley XII 60 Interscience, New York, 1994, 468-500. With more Sterically-hindered ketones or more Volatile amines, Such as O dimethyl amine, it may be preferable to employ Stronger dehydrating reagents Such as titanium chloroamides, which may be generated in Situ from titanium tetrachloride and the 65 condensation amine. This technique has been previously disclosed in R. Carlson, A. Nilsson, Acta Chemica Scandinavica, B 38, 1984, 49-53. US 6,555,634 B1 10 Subsequent formation of the Substituted ligand groups n-butyllithium, S-butyllithium, t-butyllithium, and ultimately the metal complexes themselves uses con phenyllithium, methyl magnesium chloride, ethyl magne ventional organometallic Synthetic procedures. Neutral Sium bromide, i-propyl magnesium chloride, amino-Substituted indenes may be prepared directly by dibutylmagnesium, (butyl)(ethyl)magnesium, dihexylmag contacting a ketone with titanium tetraamide in an inert nesium, Group 1 or Group 2 metals, Such as lithium, Sodium, diluent at a temperature from 25 to 150 C. potassium and magnesium, Group 1, Group 2 or Group 13 Desirably, the Substituted indenes and intermediates pre metal hydrides, Such as lithium hydride, Sodium hydride, pared according to the invention are highly pure and free of potassium hydride or lithium aluminum hydride; Group 1 or ketone starting reactants, Aldol by-products, and higher Group 2 metal amide complexes, Such as lithium weight reaction products which typically accompany prod diisopropylamide, lithium dimethylamide, lithium uct formation. Desirably the intermediate products may be hexamethyidisilazide, Sodamide and magnesium diisopro Subjected to purification procedures Such as chromato pylamide. graphic purification, distillation, recrystallization, or other BaseS of Suitable Strength for the preparation of the Suitable technique to produce the desired purity in the final anionic Salts of the invention include the foregoing as well product. Rapid distillation of polyamine compounds is pre 15 as Group 1 or Group 2 metal alkoxide complexes, Such as ferred to prevent thermal polymerization at elevated tem Sodium ethoxide, Sodium t-butoxide, potassium butoxide peratures. and potassium amylate. Conversion of the Substituted indenyl ligand to its corre The metallation of the dianionic Salt may be accomplished sponding anionic Salt may be accomplished by reaction with by methods cited in this art as well. Reaction of the dianionic an appropriate base of Suitable Strength in an appropriate salt with TiCls.(THF), followed by oxidation with methyl noninterfering Solvent. Under anaerobic, anhydrous ene chloride or lead dichloride, Substantially according to conditions, the Salt may be filtered, washed and dried in the technique of Chem. Ber., 1996, 129, 1429-1431 or nearly quantitative yield. EP-A-514.828 affords the titanium (IV) dichloride complex The formation of ligands containing the -Z-functional in very high yield. The dichloride may thereafter be silylated group from the Substituted indene metal compounds may be 25 or hydrocarbylated by ligand exchange with an appropriate accomplished by reaction with an electrophile Such as a silylating or hydrocarbylating agent, Such as methyllithium, halogenated Secondary alkylamine or halogenated Second methyl magnesium chloride, benzyl potassium, allyl lithium, ary Sillylamine to give the corresponding alkylamine or trimethylsilylmethyl lithium, neopentyl magnesium bromide silylamine Substituted compound. Suitable halogenated Sec and phenyllithium. ondary alkylamines or halogenated Secondary Sillylamines A general method for producing the titannium(II) diene include (t-butyl)(chlorodimethylsilyl)amine, (t-butyl) complex from the corresponding titanium(IV) dichloride (chloro dimethylsily limethyl)amine, (t-butyl) preferably involves the treatment of the dichloride with (bromomethyidimethylsilyl)amine, (t-butyl)(2-chloroethyl) n-butyl lithium in the presence of an appropriate diene. A amine, (chlorodimethylsilyl)(phenyl)amine, (adamantyl) Similar technique has been described in Organometallics, (chlorodiphenyisilyl)amine, (chlorodimethylsilyl) 35 1995, 14, 3132-3134 as well as in U.S. Pat. No. 5,556,928. (cyclohexyl)amine, (benzyl)(chlorodimethylsilyl)amine and The formation of the metal complexes wherein the metal (t-butyl)(chloromethylphenylsilyl)amine. The technique is is in the +3 formal oxidation State according to the invention based upon the anion alkylation method previously dis can be accomplished by any of Several Synthesis methods. closed by WO93/08199 and Organometallics, 1996, 15(6), One technique involves the reaction under anaerobic and 1572-81. In a preferred embodiment, the lithio derivative of 40 anhydrous conditions of the dianionic Salts with trivalent the anionic Salt is slowly added to a molar excess of metal Salts, Such as Group 4 metal (III) halide or alkoxide (t-butyl)(chlorodimethylsilyl)amine in an ether solvent. This complexes, optionally followed by Sillylation or hydrocar ligand may also be converted to its insoluble anionic Salt by bylation with Suitable silylating or hydrocarbylating agents, reaction of the free base with two equivalents of a base of to form the corresponding halide, alkoxide, Silyl or hydro Suitable Strength in an appropriate noninterfering Solvent. 45 carbyl complexes of the invention. A further Synthesis By the term “appropriate noninterfering Solvent' is meant method involves reducing an appropriate metal (IV) com a solvent that doesn't interfere with the formation of, or react plex with a Suitable reducing agent to the corresponding deleteriously with, the desired product. Such solvents suit metal (III) complex. Suitable reducing agents especially able for the preparation of the anionic Salts of the invention include Zinc, aluminum, lithium, and magnesium. include, but are not limited to aliphatic and aromatic 50 Suitable Sillylating and hydrocarbylating agents for the hydrocarbons, particularly Straight and branched chain metal complexes of the invention include the corresponding hydrocarbons Such as butane, pentane, hexane, heptane, silyl or hydrocarbyl derivatives of Group 1, 2 or 13 metals octane, decane, including their branched isomers and mix or Group 2 metal halides, preferably lithium Sodium, tures thereof; cyclic and alicyclic hydrocarbons Such as potassium, magnesium and aluminum, or Group 2 metal cyclohexane, cycloheptane, methylcyclohexane, methylcy 55 Grignards. Examples of Suitable hydrocarbyl and Silyl cloheptane and mixtures thereof; aromatic and hydrocarbyl groups include alkyl, Such as methyl, ethyl, propyl, butyl, Substituted aromatic compounds Such as benzene, toluene, neopentyl and hexyl, aryl, Such as phenyl, naphthyl and Xylene, ethylbenzene, diethylbenzene and mixtures thereof; biphenyl, aralkyl, Such as benzyl, tolylmethyl, diphenylm ethers and cyclic ethers, particularly Ce dialkyl ethers, ethyl, alkaryl, Such as tolyl and Xylyl; allyl; Sillyl- or alkyl such as diethyl ether, dibutyl ether and methyl-t-butyl ether, 60 substituted allyl, such as methylallyl, trimethylsilylallyl, C. dialkyl ether derivatives of (poly)alkylene glycols, Such dimethylallyl and trimethylallyl, trialkylsilyl, such as trim as dimethoxyethane, and dioxane and THF and mixtures ethylsilyl and triethylsilyl; trialkylsilylalkyl, such as trim thereof. Mixtures of the foregoing are also Suitable. ethylsilylmethyl; pentadienyl; alkyl- or silyl-substituted BaseS of Suitable Strength for the preparation of the pent a die nyl, Such as methylp ent a die nyl, dianionic salts of the invention include hydrocarbyl salts of 65 dimethylpentadienyl, trimethylsilylpentadienyl, bis Group 1 and Group 2 metals, especially alkyl or aryl Salts of (trimethylsilyl)pentadienyl, cyclohexadienyl and dimethyi lithium or magnesium, Such as methyllithium, ethyllithium, cyclohexadienyl, dialkylaminoalkaryl, Such as O-(N,N- US 6,555,634 B1 11 12 dimethylaminomethyl)phenyl; and dialkylaminoaralkyl, a compatible, noncoordinating anion, A. AS used herein, the such as o-(N,N-dimethylamino)benzyl. Preferred silylating term "noncoordinating means an anion or Substance which and hydrocarbylating agents include trimethylaluminum, either does not coordinate to the metal complex and the methyllithium, methyl magne Sium chloride, catalytic derivative derived therefrom, or which is only neopentyllithium, trimethylsilylmethylmagnesiumchloride weakly coordinated to Such complexes thereby remaining and phenyllithium. Stabilizing group-containing hydrocar sufficiently labile to be displaced by a neutral Lewis base. A bylating agents are also included, especially the Stabilizing noncoordinating anion Specifically refers to an anion which group-containing hydrocarbylating agents and Salts of the Stabilizing group-containing hydrocarbyl groups described when functioning as a charge balancing anion in a cationic in U.S. Pat. No. 5,504,224, whose salts include, for example, metal complex does not transfer an anionic Substituent or benzyl potassium, 2-(N,N-dimethylamino)benzyllithium, fragment thereof to Said cation thereby forming neutral allyllithium and dimethylpentadienyl potassium. Such sta complexes. “Compatible anions are anions which are not bilizing groups are further described in U.S. Pat. No. 5,374, degraded to neutrality when the initially formed complex 696, and elsewhere. decomposes and are noninterfering with desired Subsequent The complexes are rendered catalytically active by com 15 polymerization or other uses of the complex. bination with an activating cocatalyst or by use of an Preferred anions are those containing a Single coordina activating technique. Suitable activating cocatalysts for use tion complex comprising a charge-bearing metal or metal herein include polymeric or oligomeric alumoxanes, espe loid core which anion is capable of balancing the charge of cially methylalumoxane, triisobutyl aluminum-modified the active catalyst Species (the metal cation) which may be methylalumoxane, or isobutylalumoxane; neutral Lewis formed when the two components are combined. Also, Said acids, Such as Cas hydrocarbyl Substituted Group 13 anion should be sufficiently labile to be displaced by ole compounds, especially tri(hydrocarbyl)aluminum- or tri finic, diolefinic and acetylenically unsaturated compounds (hydrocarbyl)boron-compounds and halogenated (including or other neutral Lewis bases Such as ethers or nitriles. perhalogenated) derivatives thereof, having from 1 to 15 Suitable metals include, but are not limited to, aluminum, carbons in each hydrocarbyl or halogenated hydrocarbyl 25 gold and platinum. Suitable metalloids include, but are not group, more especially perfluorinated tri(aryl)boron limited to, boron, phosphorus, and Silicon. Compounds compounds, and most especially tris(o-nonafluorobiphenyl) containing anions which comprise coordination complexes borane, tris(pentafluorophenyl)borane; nonpolymeric, compatible, noncoordinating, ion forming compounds containing a single metal or metalloid atom are, of course, (including the use of Such compounds under oxidizing well known and many, particularly Such compounds con conditions), especially the use of ammonium-, taining a single boron atom in the anion portion, are avail phosphonium-, Oxonium-, carbonium-, Sillylium- or able commercially. Sulfonium-salts of compatible, noncoordinating anions, or Preferably such cocatalysts may be represented by the ferrocenium Salts of compatible, noncoordinating anions, following general formula: bulk electrolysis (explained in more detail hereinafter); and 35 combinations of the foregoing activating cocatalysts and techniques. The foregoing activating cocatalysts and acti Vating techniques have been previously taught with respect wherein: to different metal complexes in EP-A-277,003 and U.S. Pat. L* is a neutral Lewis base; No. 5,153,157, U.S. Pat. No. 5,064,802, U.S. Pat. No. 40 (L*-H)" is a Bronsted acid; 5,321,106, and U.S. Pat. No. 5,721,185. (A) is a noncoordinating, compatible anion having a Combinations of neutral Lewis acids, especially the com charge of d-, and bination of a trialkyl aluminum compound having from 1 to d is an integer from 1 to 3. 4 carbons in each alkyl group and a halogenated tri More preferably (A) corresponds to the formula: (hydrocarbyl)boron compound having from 1 to 20 carbons 45 in each hydrocarbyl group, especially tris M'Q; (pentafluorophenyl)borane, tris(o-nonafluorobiphenyl) wherein: borane, further combinations of Such neutral Lewis acid M" is boron or aluminum in the +3 formal oxidation state; mixtures with a polymeric or oligomeric alumoxane, and and combinations of a single neutral Lewis acid, especially 50 Q independently each occurrence is Selected from tris(pentafluorophenyl)borane with a polymeric or oligo hydride, dialkylamido, halide, hydrocarbyl, meric alumoxane are especially desirable activating cocata hydrocarbyloxide, halosubstituted-hydrocarbyl, halo lysts. A benefit according to the present invention is the Substituted hydrocarbyloxy, and halo-substituted silyl discovery that the most efficient catalyst activation using hydrocarbyl radicals (including perhalogenated Such a combination of tris(pentafluorophenyl)borane/ 55 hydrocarbyl-perhalogenated hydrocarbyloxy- and per alumoxane mixture occurs at reduced levels of alumoxane. halogenated silylhydrocarbyl radicals), said Q having Preferred molar ratios of metal complex: tris up to 20 carbons with the proviso that in not more than (pentafluorophenyl)borane: alumoxane are from 1:1:1 to one occurrence is Q halide. Examples of Suitable 1:5:5, more preferably from 1:1:1.5 to 1:5:3. The Surprising hydrocarbyloxide Q groups are disclosed in U.S. Pat. efficient use of lower levels of alumoxane with the present 60 No. 5,296,433. invention allows for the production of olefin polymers with In a more preferred embodiment, d is one, that is, the high catalytic efficiencies using less of the expensive alu counterion has a Single negative charge and is A. Activating moxane cocatalyst. Additionally, polymers with lower levels cocatalysts comprising boron which are particularly useful of aluminum residue, and hence greater clarity, are obtained. in the preparation of catalysts of this invention may be Suitable ion forming compounds useful as cocatalysts in 65 represented by the following general formula: one embodiment of the present invention comprise a cation which is a Bronsted acid capable of donating a proton, and US 6,555,634 B1 13 14 wherein: tri(2,6-dimethylphenyl) phosphonium tetrakis L* is as previously defined; (pentafluorophenyl)borate. B is boron in a formal oxidation state of 3; and Preferred are tetrakis(pentafluorophenyl)borate salts of Q is a hydrocarbyl-, hydrocarbyloxy-, fluorinated long chain alkyl mono- and disubstituted ammonium hydrocarbyl-, fluorinated hydrocarbyloxy-, or fluori 5 complexes, especially C-C alkyl ammonium complexes, nated Sillylhydrocarbyl-group of up to 20 nonhydrogen especially methyldi(octadecyl)ammonium tetrakis atoms, with the proviso that in not more than one (pentafluorophenyl)borate and methyldi(tetradecyl) occasion is Q hydrocarbyl. ammonium tetrakis(pentafluorophenyl)borate. Most preferably, Q is each occurrence a fluorinated aryl Especially preferred activating cocatalysts are tris group, especially, a pentafluorophenyl group. (pentafluorophenyl)borane, (R'NHCH)"(CHOH) B Illustrative, but not limiting, examples of ion forming (CF), (R'NHCH)"B(CF), or (CH)NHR'B compounds comprising proton donatable cations which may (CFS), where R' independently each occurrence is a Substituted or unsubstituted Saturated hydrocarbyl group be used as activating cocatalysts in the preparation of the having from 12 to 30 carbon atoms, and R independently catalysts of this invention are tri-Substituted ammonium Salts 15 Such as: each occurrence is a Substituted or unsubstituted Saturated hydrocarbyl group having from 1 to 8 carbon atoms. trimethylammonium tetraphenylborate, Another Suitable ion forming, activating cocatalyst com methyidioctadecylammonium tetraphenylborate, prises certain imidazolide, Substituted imidazolide, triethylammonium tetraphenylborate, imidazolinide, Substituted imidazolinide, benzimidazolide, tripropylammonium tetraphenylborate, or Substituted benzimidazolide anions depicted Schemati tri(n-butyl)ammonium tetraphenylborate, cally as follows: methyltetradecyloctadecylammonium tetraphenylborate, N,N-dimethylanilinium tetraphenylborate, R3 N,N-diethylanilinium tetraphenylborate, 25 N,N-dimethyl(2,4,6-trime thy lanilinium) tetraphenylborate, clf trimethylammonium tetrakis(pentafluorophenyl)borate, R3 R3 triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(pentafluorophenyl)borate, R3 tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammonium tetrakis(pentafluorophenyl) A-J-1-N1 y N-I-1 or borate, 35 N,N-dimethylanilinium tetrakis(pentafluorophenyl) (R)2 (R)2 borate, N,N-diethylanilinium tetrakis(pentafluorophenyl)borate, R3 N,N-dimethyl(2,4,6-trimethylanilinium) tetrakis (pentafluorophenyl)borate, 40 trimethylammonium tetrakis(2,3,4,6-tetrafluorophenyl) re-6- borate, triethylammonium tetrakis(2,3,4,6-tetrafluorophenyl) borate, 45 tritopylammonium tetrakis(2,3,4,6-tetrafluorophenyl) R3 R3 borate, tri(n-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl) borate, wherein: dimethyl(t-butyl)ammonium tetrakis(2,3,4,6- 50 A*" is a monovalent cation, preferably a trihydrocarbyl tetrafluorophenyl)borate, ammonium cation, containing one or two Colo alkyl N,N-dimethyla nilinium tetrakis (2,3,4,6- groups, especially the methylbis(tetrade cyl) tetrafluorophenyl)borate, ammonium- or methylbis(octadecyl)ammonium N,N-diethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl) cation, borate, and 55 R, independently each occurrence, is hydrogen or a halo, N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis(2,3,4,6- hydrocarbyl, halo carbyl, halohydrocarbyl, tetrafluorophenyl)borate. silylhydrocarbyl, or silyl, (including mono-, di- and Dialkyl ammonium Salts. Such as: tri(hydrocarbyl)silyl) group of up to 30 atoms not di-(i-propyl)ammonium tetrakis(pentafluorophenyl) counting hydrogen, preferably C-2 alkyl, and 60 J* is tris(pentafluorophenyl)borane or tris borate, and (pentafluorophenyl)alumane). dicyclohexylammonium tetrakis(pentafluorophenyl) Another Suitable ion forming, activating cocatalyst com borate. prises a Salt of a cationic oxidizing agent and a Tri-Substituted phosphonium Salts. Such as: noncoordinating, compatible anion represented by the for triphenylphosphonium tetrakis(pentafluorophenyl)borate, 65 mula: tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl) borate, and (OX')(A), US 6,555,634 B1 15 16 wherein: prepared from inert conductive materials, by which are OX is a cationic oxidizing agent having a charge of e--, meant conductive materials that are unaffected by the reac tion mixture or reaction conditions. Platinum or palladium e is an integer from 1 to 3; and are preferred inert conductive materials. Normally an ion A and d are as previously defined. permeable membrane Such as a fine glass frit Separates the Examples of cationic oxidizing agents include: cell into Separate compartments, the working electrode com ferrocenium, hydrocarbyl-Substituted terrocenium, Ag" and partment and counter electrode compartment. The working Pb". Preferred embodiments of A are those anions pre electrode is immersed in a reaction medium comprising the viously defined with respect to the Bronsted acid containing metal complex to be activated, Solvent, Supporting activating co cataly St S, especially tetrak is electrolyte, and any other materials desired for moderating (pentafluorophenyl)borate. the electrolysis or Stabilizing the resulting complex. The Another Suitable ion forming, activating cocatalyst com counter electrode is immersed in a mixture of the Solvent and prises a compound which is a Salt of a carbenium ion and a Supporting electrolyte. The desired Voltage may be deter noncoordinating, compatible anion represented by the for mined by theoretical calculations or experimentally by mula: Sweeping the cell using a reference electrode Such as a Silver 15 electrode immersed in the cell electrolyte. The background (C)"A cell current, the current draw in the absence of the desired electrolysis, is also determined. The electrolysis is com wherein: pleted when the current drops from the desired level to the (C)" is a C-20 carbenium ion; and background level. In this manner, complete conversion of A is as previously defined. A preferred carbenium ion is the initial metal complex can be easily detected. Suitable the trityl cation, that is, triphenylmethylium. Supporting electrolytes are Salts comprising a cation and a A further Suitable ion forming, activating cocatalyst com compatible, noncoordinating anion, A. prises a compound which is a Salt of a Sillylium ion and a Preferred Supporting electrolytes are Salts corresponding noncoordinating, compatible anion represented by the for to the formula GA; mula: 25 wherein: G" is a cation which is nonreactive towards the starting RSiA and resulting complex, and wherein: A is as previously defined. R is Co hydrocarbyl, and A are as previously defined. Examples of cations, G", include tetrahydrocarbyl Sub Preferred Sillylium Salt activating cocatalysts are trimeth Stituted ammonium or phosphonium cations having up to 40 ylsilylium tetrakispentafluorophenylborate, triethylsilylium nonhydrogen atoms. Preferred cations are the tetra(n- tetrakispentafluorophenylborate and ether Substituted butylammonium)- and tetraethylammonium-cations. adducts thereof. Sillylium Salts have been previously generi During activation of the complexes of the present inven cally disclosed in J. Chem Soc. Chem. Comm., 1993, tion by bulk electrolysis the cation of the Supporting elec 383-384, as well as Lambert, J. B., et al., Organometallics, 35 trolyte passes to the counter electrode and A migrates to the 1994, 13, 2430-2443. The use of the above silylium salts as working electrode to become the anion of the resulting activating cocatalysts for addition polymerization catalysts oxidized product. Either the solvent or the cation of the is disclosed in U.S. Pat. No. 5,625,087. Supporting electrolyte is reduced at the counter electrode in Certain complexes of alcohols, mercaptains, Silanols, and equal molar quantity with the amount of oxidized metal Oximes with tris(pentafluorophenyl)borane are also effective 40 complex formed at the working electrode. Preferred Sup catalyst activators and may be used according to the present porting electrolytes are tetrahydrocarbylammonium Salts of invention. Such cocatalysts are disclosed in U.S. Pat. No. tetrakis(perfluoroaryl)borates having from 1 to 10 carbons in 5,296,433. each hydrocarbyl or perfluoroaryl group, especially tetra(n- The technique of bulk electrolysis involves the electro butylammonium) tetrakis-(pentafluorophenyl)borate. chemical oxidation of the metal complex under electrolysis 45 A further recently discovered electrochemical technique conditions in the presence of a Supporting electrolyte com for generation of activating cocatalysts is the electrolysis of prising a noncoordinating, inert anion. In the technique, a disilane compound in the presence of a Source of a Solvents, Supporting electrolytes and electrolytic potentials noncoordinating compatible anion. This technique is more for the electrolysis are used Such that electrolysis byproducts fully disclosed in U.S. Pat. No. 5,372,682. that would render the metal complex catalytically inactive 50 The foregoing electrochemical activating technique and are not Substantially formed during the reaction. More activating cocatalysts may also be used in combination. An particularly, Suitable Solvents are materials that are: liquids especially preferred combination is a mixture of a tri under the conditions of the electrolysis (generally tempera (hydrocarbyl)aluminum or tri(hydrocarbyl)borane com tures from 0 to 100° C.), capable of dissolving the Support pound having from 1 to 4 carbons in each hydrocarbyl group ing electrolyte, and inert. "Inert Solvents' are those that are 55 with an oligomeric or polymeric alumoxane compound. not reduced or oxidized under the reaction conditions The molar ratio of catalyst/cocatalyst employed prefer employed for the electrolysis. It is generally possible in View ably ranges from 1:10,000 to 100:1, more preferably from of the desired electrolysis reaction to choose a Solvent and 1:5000 to 10:1, most preferably from 1:1000 to 1:1. a Supporting electrolyte that are unaffected by the electrical Alumoxane, when used by itself as an activating cocatalyst, potential used for the desired electrolysis. Preferred solvents 60 is employed in large quantity, generally at least 100 times the include difluorobenzene (all isomers), dimethoxyethane quantity of metal complex on a molar basis. Tris (DME), and mixtures thereof. (pentafluorophenyl)borane, where used as an activating The electrolysis may be conducted in a Standard electro cocatalyst, is employed in a molar ratio to the metal complex lytic cell containing an anode and cathode (also referred to of form 0.5:1 to 10:1, more preferably from 1:1 to 6:1, most as the working electrode and counter electrode respectively). 65 preferably from 1:1 to 5:1. The remaining activating cocata Suitable materials of construction for the cell are glass, lysts are generally employed in approximately equimolar plastic, ceramic and glass coated metal. The electrodes are quantity with the metal complex. US 6,555,634 B1 17 18 Suitable polymerizable monomers include ethylenically EXAMPLE 1. unsaturated monomers, acetylenic compounds, conjugated or non-conjugated dienes, and polyenes. Preferred mono mers include olefins, for examples alpha-olefins having from Preparation of Dichloro(N-(1,1-dimethylethyl)-1- 2 to 20,000, preferably from 2 to 20, more preferably from 5 (1,2,3,3a,7a-m)-5-methoxy-3-(1-pyrrolidino)-1H 2 to 8 carbon atoms and combinations of two or more of Such inden-1-yl)-1,1-dimethylsilanaminato(2-)-N) titanium alpha-olefins. Particularly Suitable alpha-olefins include, for example, ethylene, propylene, 1-butene, 1-pentene, Step 1 Preparation of 1-(5-Methoxy-1H-inden-3-yl) 4-methylpentene-1,1-hexene, 1-heptene, 1-octene, pyrrolidine. 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, or combinations thereof, as well as long chain vinyl terminated oligomeric or polymeric reaction products formed during the polymerization, and Co C-olefins specifically added to the reaction mixture in order to produce relatively long chain branches in the 15 resulting polymers. Preferably, the alpha-olefins are ethylene, propene, 1-butene, 4-methyl-pentene-1,1-hexene, 1-octene, and combinations of ethylene and/or propene with one or more of such other alpha-oletins. Other preferred monomers include Styrene, halo- or alkyl Substituted Styrenes, tetrafluoroethylene, Vinylcyclobutene, 1,4- 6-Methoxy-1-indenone (7.30 g, 45.01 mmol) was dis hexadiene, dicyclopentadiene, ethylidene norbornene, and Solved in 20 mL of toluene in a flask equipped with a 1,7-octadiene. Mixtures of the above-mentioned monomers may also be employed. Dean-Stark adapter. To this solution, 18.8 mL (225 mmol) of In general, the polymerization may be accomplished at 25 pyrrolidine was added followed by 0.5 g of POs. The conditions well known in the prior art for Solution phase, reaction mixture was refluxed for approximately 5 hours. At Slurry, gas phase and high pressure Ziegler-Natta or this time the finger of the Dean-Stark adapter (10 mL Kaminsky-Sinn type polymerization reactions. Examples of capacity) was emptied and 10 additional mL of pyrrolidine Such well known polymerization processes are depicted in were added to the flask. After 14 hrs under reflux, GC U.S. Pat. No. 5,084,534, U.S. Pat. No. 5,405,922, U.S. Pat. analysis showed complete conversion to 1-(5-methoxy-1H No. 4,588,790, U.S. Pat. No. 5,032,652, U.S. Pat. No. inden-3-yl)pyrrolidine. The flask was cooled to room tem 4,543,399, U.S. Pat. No. 4,564,647, U.S. Pat. No. 4,522,987, perature and the Solvent was evaporated in vacuum leaving and elsewhere. Preferred polymerization temperatures are a brown-red oil. This oil was dissolved in 10 mL of ether from 0-250 C. Preferred polymerization pressures are from followed by 60 mL of hexane. This solution was cooled to atmospheric to 3000 atmospheres. Molecular weight control 35 -27 C. overnight. The resulting solid was filtered off and agents can be used in combination with the present cocata the Solvent was evaporated from the Solution leaving 8.15g lysts. Examples of Such molecular weight control agents of the desired product as a red oil. Yield was 84 percent. include hydrogen, Silanes or other known chain transfer agents. The catalyst composition may be used by itself "H NMR (CD) & 1.54 (m, 4H), 3.20 (m, 4H), 3.27 (s, (homogeneously) or Supported on an inert Support Such as 40 2H), 3.47 (s, 3H), 5.09 (s, 1H), 6.75 (dd, 1H, J =8.0 Hz, Silica, alumina or a polymer. J =2.2 Hz), 7.22 (d. 1H, J, =8.0 Hz), 7.38 (d. 1H, The skilled artisan will appreciate that the invention J-2.2 Hz). C{H} NMR (CD) & 25.32,35.04, 50.19, disclosed herein may be practiced in the absence of any 55.07, 102.08, 107.77, 109.95, 124.55, 137.70, 143.98, component which has not been Specifically disclosed. The 150.47, 159.13. GC-MS: Calcd for CHNO: 215.13, following examples are provided as further illustration of the 45 found 215.15. invention and are not to be construed as limiting. Unless Stated to the contrary all parts and percentages are expressed Step 2 Preparation of (5-Methoxy-3-(1-pyrrolidino)-1H on a weight basis. Where Stated, the term "room tempera inden-1-yl)lithium ture” refers to a temperature from 20 to 25 C., the term “overnight” refers to a time from 12 to 18 hours, and the 50 term “mixed alkanes' refers to a mixture of propylene oligomerS Sold by EXXon Chemicals Inc. under the trade designation IsoparTM E. N H and 'C NMR spectra were recorded on a Varian XL (300 MHz) spectrometer. Chemical shifts were determined 55 relative to TMS or through the residual CHCl in CDC1 or O) the residual CHD in CD, relative to TMS. Solvents were used following passage through double columns charged Li with activated alumina and alumina Supported mixed metal oxide catalyst (Q-50R) catalyst, available from Engelhard 60 Corp.). The compounds n-BuLi, Grignard reagents were all 1-(5-methoxy-1H-inden-3-yl)pyrrolidine (8.15 g., 37.9 used as purchased from commercial Sources in an appropri mmol) was dissolved in 80 mL of hexane and 23.7 mL of 1.6 ate Solvent and used as received. All Syntheses were per M n-BuLi were added dropwise via syringe over a 5 min formed under dry nitrogen atmosphere using a combination period giving an orange precipitate. The reaction mixture of glove box and high Vacuum techniques. The drawings of 65 was stirred for 2 h, filtered, washed with 60 mL of hexane lithium complexes are simplified and are not intended to and allowed to dry in vacuum to afford the desired product accurately represent the compounds hapticity. as a orange Solid (7.26 g., 87 percent yield). US 6,555,634 B1 19 20 Step 3 Preparation of N-(1,1-Dimethylethyl)-1-(5-methoxy Step 5 Preparation of Dichloro(N-(1,1-dimethylethyl-1-((1, 3-(1-pyrrolidino)-1H-inden-1-yl)-1,1-dimethylsilanamine 2,3,3a,7a-m)-5-methoxy-3-(1-pyrrolidino)-1H-inden-1-yl)- 1,1-dimethylsilanaminato(2-)-N)titanium

CH / O

1O O O)

HCIly, Si T I ICI 15 HC \ / No N (5-Methoxy-3-(1-pyrroldino)-1H-inden-1-yl)lithium (4.00 g, 18.08 mmol) was dissolved in 40 mL of THF and HC-7(HC CH added dropwise to a solution of N-(tert-butyl)-N-(1-chloro 1,1-dimethylsilyl)amine (4.2 g, 25.3 mmol) in 120 mL of 4.68 g (12.6 mmol) Of TiCl(THF) were suspended in 80 THF over a 25 min period, with stirring continued for 24 h. mL of THF. To this solution, 4.5 g (12.6 mmol) of (1-(((1, The Solution was evaporated in vacuum to give a dark red oil 1-imethylethyl)amino)dimethylsilyl)-5-methoxy-3-(1- which was dissolved in hexane (40 mL). LiCl was filtered pyrrolidino)-1H-inden-1-yl)lithium dissolved in 40 mL of from this solution and the Solvent was removed in under 25 THF were added within 5 min. The Solution was then stirred vacuum to give 6.20 g of product as a dark red oil. (99 for 50 min. After this time, 2.28 g of PbCl (8.21 mmol) percent yield). were added and the Solution was stirred for 12 h. The THF was then removed under reduced pressure. The residue was then extracted with 120 mL of toluene, the Solution was "H NMR (CD) 8 -0.03 (s, 3H), 0.08 (s, 3H), 0.57 (s, filtered, and the toluene was removed under reduced pres 1H), 1.12 (s, 9H), 1.66 (m, 4H), 3.24 (m, 4H), 3.34 (d. 1H, Sure. The residue was then titrated with 60 mL of hexane and J =1.8 Hz), 3.51 (s.3H), 5.41 (d. 1H, J = 1.8 Hz), 6.84 the precipitate was collected via filtration on a frit, washed with 60 mL of hexane and dried under vacuum to yield 3.87 (dd, 1H, J, -8.3 Hz, J-2.2 Hz), 7.35 (d. 1H, J, ,- g of dichloro(N-(1,1-dimethylethyl)-1-((1,2,3,3a,7a-m)-5- 2.2 Hz), 7.46 (d. 1H, J =8.3 Hz), "C{H} NMR (CD) 35 methoxy-3-(1-pyrrollidino)-1H-inden-1-yl)-1,1- 8 -0.76, 0.33, 25.22, 34.03, 42.57, 49.50, 50.72, 55.05, dimethylsilanaminato(2-)-N)titanium as a black microcrys 106.62, 106.68, 110.33, 124.05, 139.19, 142.75, 149.36, talline solid. Yield was 66 percent. 158.13. H NMR (CD) 8 0.54 (s.3H), 0.61 (s.3H), 1.39 (s.9H), 1.54 (m, 4H), 3.32 (s, 2H), 3.40 (s, 3H), 3.68 (m, 2H), 5.68 40 (s, 1H), 6.97 (s, 1H), 6.99 (d. 1H, J, -9.1 Hz), 7.48 (d. Step 4 Preparation of (1-(((1,1-Dimethylethyl)amino) 1H, J, =9.1 Hz). 'C{H} NMR (CD) & 1.46, 3.58, dimethylsilyl)-5-methoxy-3-(1-pyrrolidino)-1H-inden-1-yl) 25.82, 33.00, 50.52, 55.06, 60.73, 92.75, 103.48, 107.76, lithium, Lithium Salt 122.61, 129.25, 130.21, 130.40, 148.86, 160.35.

45 EXAMPLE 2 Preparation of (N-(1,1-Dimethylethyl)-1-((1,2,3,3a, N 7a-m)-5-methoxy-3-(1-pyrrolidinyl)-1H-inden-1-yl)- MeO 1,1-dimethylsilanaminato(2-)-N)dimethyltitanium 50 HC-O -CH3 Li Si Ho1 V LN-t-Bu 55

6.2 g (18.0 mmol) N-(1,1-dimethylethyl)-1-(5-methoxy H3CSi Til ICHo 3-(1-pyrrolidino)-1H-inden-1-yl)-1,1-dimethylsilanamine E 1 \ Yoh, were combined with 80 mL of hexane. To this solution 24.7 60 N mL (39.6 mmol) of n-BuLi (1.6 M) were added dropwise. Upon complete addition of the n-BuLi, the solution was HC-7( Stirred for 5 hat room temperature. The resulting precipitate HC CH was collected via filtration, washed with 60 mL of hexane to 65 give 6.45 g of the desired product as a yellow solid. Yield 0.70 g (1.5 mmol) Of dichloro(N-(1,1-dimethylethyl)-1- was 98 percent. (1,2,3,3a,7a-m)-5-methoxy-3-(1-pyrrolidinyl)-1H-inden-1- US 6,555,634 B1 21 22 yl)-1,1-dimethylsilanaminato(2-)-N) titanium were partly EXAMPLE 4 dissolved in 50 mL of EtO. To this solution, 1.06 mL (3.2 Preparation of Chloro(cyclopentadienyl)(N-(1,1- mmol) of MeMgI (3.0 M) were added dropwise while dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-m)-5- Stirring over a 5-minute period. The Solution changed color methoxy-3-(1-pyrrolidino)-1H-inden-1-yl) from black to dark red. After the addition of MeMgI was Silanaminato(2-)-N)titanium completed, the solution was stirred for 60 minutes. EtO was removed under reduced pressure and the residue was extracted with hexane (2x20 mL), the solution was filtered y H. and the filtrate was evaporated to dryneSS under reduced O preSSure to give 0.450 g of the dimethyl titanium complex (71 percent yield) as a red Solid. "H NMR (CD) 8 0.15 (s.3H), 0.50 (s.3H), 0.63 (s.3H), C. O) 0.79 (s, 3H), 1.53 (s, 9H), 1.58 (m, 4H), 3.43 (m, 2H), 3.43 15 (s, 3H), 3.51 (m, 3H), 5.49 (s, 1H), 6.88 (dd, 1H, J =9.1 Hz, J-1.9 Hz), 7.11 (d. 1H, J, -1.9 Hz), 7.39 11 (d. HCI, Si T. C. 1H, J =9.1 Hz). "C{H} NMR (CD) & 2.29, 444, fy \ / Yous 25.96, 34.70, 48.49, 50.53, 53.78, 54.87, 57.77, 83.72, N 102.52, 105.64, 119.36, 125.97, 129.52, 143.60, 158.37. theHd 7. CH EXAMPLE 3

Preparation of Cyclopentadienyl(N-(1,1- 25 0.2052 g of cyclopentadienyl(N-(1,1-dimethylethyl)-1,1- dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-m)-5- dimethyl-1-((1,2,3,3a,7a-m)-5-methoxy-3-(1-pyrrolidinyl)- methoxy-3-(1-pyrrolidino)-1H-inden-1-yl) 1H-inden-1-yl)silanaminato(2-)-N) titanium (0.450 mmol) were mixed with about 6 mL of CH2Cl2. The color changed Silanaminato(2-)-N)titanium instantly to an intense purple. The reaction mixture was stirred for several hours, the solvent was removed under CH Vacuum, the residue was extracted with hexane, filtered and O the Solvent was removed under reduced preSSure to give 0.0688 g of the desired complex as an extremely intensely colored purple powder (31.1 percent yield). 35 "H (CD) 8 0.51 (s, 3H), 0.65 (s.3H), 1.18 (br, 4H), 1.35 (s, 9H), 3.20 (br, 2H), 3.46 (s, 3H), 3.55 (br, 2H), 5.78, (s, 5H), 5.87, (s, 1H), 6.89 (d. 1H, J =8.5 Hz), 6.93 (s, 1H), CO 7.25 (d. 1H, J =8.6 Hz). C (CD) & 167.5, 155.4, HCyS 152.7, 126.9, 1216, 116.6, 115.2, 107.9, 94.6, 89.1, 60.9, 40 55.3, 50.7, 33.0, 25.2, 3.9, 2.9. MS: Calcd for N CHCINSiTi: 490.2 Found: 490.1. the 7. EXAMPLE 5 HC oCH Preparation of (1-((1,2,3,3a,7a-m)-5-Methoxy-3- 45 (pyrrolidinyl)-1H-inden-1-yl)-N-(1,1- dimethylethyl)-1,1-dimethylsilanaminato(2-)-N)((2- To a well-stirred solution of 2.822 g of bis (dimethylamino-N)phenyl)methyl-C)titanium (cyclopentadienyl)titanium chloride (13.22 mmol) in about 120 mL of THF were slowly added 4.900 g of the dilithium CH salt of (N-(1,1-dimethylethyl)-1,1-dimethyl-1-(5-methoxy 50 3-pyrrolidino-1H-inden-1-yl)silanamine (96 percent pure, 13.22 mmol) as a powder over the course of about 30 minutes. The reaction mixture changed from green to yellow-brown and was stirred overnight. The solvents were 55 removed under reduced pressure and the residue was extracted with hexane and the resulting Solution was filtered to give a yellow-brown-greenish Solution. The product was fractionated and the first fraction was reextracted with hexane and refiltered. The Solvent was removed to give a 60 dark Solid. This product was slurried in hexane, chilled in a freezer overnight, then filtered and the solids were washed with cold hexane, then dried under reduced pressure to yield 1.223 g of the desired product as a dark olive green powder. 65 ESR showed a signal at g=1.978 consistent with a Ti(III) To a solution of 0.5567 g of cyclopentadienyl(N-(1,1- complex. Magnetic Susceptibility (Evans method): 1.62 u. dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-m)-5-methoxy US 6,555,634 B1 23 24 3-(1-pyrrolidinyl)-1H-inden-1-yl)silanaminato(2)-N) EXAMPLE 7 titanium (1.222 mmol) in about 40 mL of EtO was slowly added 0.1811 g of (2-(N,N-dimethylamino)benzyl)lithium Preparation of Dichloro(1-((1,2,3,3a,7a-m)-5,6- (1.283 mmol) slurried in about 15 mL of EtO. The dark dimethoxy-3-(1-pyrrolidinyl)-1H-inden-1-yl)-N-(1, reddish-olive green/brown reaction mixture was stirred 1-dimethylethyl)-1,1-dimethylsilanaminato(2-)-N) overnight. An additional 0.0156 g of (2-(N,N- titanium dimethylamino)benzyl)lithium (total 1.394 mmol) was added. After Stirring overnight once more and removing the Step 1 Preparation of 1-(5,6-Dimethoxy-1H-inden-3-yl) Solvent under reduced pressure, the residue was extracted pyrrolidine with hexane, filtered and concentrated to dryness. About 5 mL of hexane were added to dissolve the product and the Solution was placed in the freezer. The Supernatant was removed and the black Solid remaining was dried under N reduced pressure. The yield of product as a black Solid was 15 MeO 0.3418 g., 53.3 percent.

MS: Calcd. for CHNOSiTi: 524.3. Found: 523.3. MeO ESR analysis was consistent with a Ti(III) complex. Magnetic Susceptibility (Evans method): 1.57 u. 5,6-Dimethoxy-1-indenone (5.1 g, 26.53 mmol) was dis solved in 120 mL of toluene. To this solution 17.7 mL (212 EXAMPLE 6 mmol) of pyrrolidine was added followed by 0.5g of POs. Preparation of Chloro(1-((1,2,3,3a,7a-m)-5- The reaction mixture was refluxed for about 20 hours in a methoxy-3-pyrrolidinyl-1H-inden-1-yl)-N-(1,1- 25 flask equipped with a Dean-Stark adapter. The flask was dimethylethyl)-1,1-dimethylsilanaminato(2-)-N)((2- cooled to room temperature and the Solvent was evaporated (dimethylamino)phenyl)methyl)titanium in vacuum leaving a brown-red Solid. This Solid was extracted with 50 mL of ether and filtered. The ether was y H. evaporated leaving a brown Solid. This Solid was extracted O with 120 mL of hot hexane and filtered. The hexane was removed and Solid was dissolved in a mixture of 30 mL of toluene and 60 mL of hexane and filtered. The red solution was cooled to -27 C. overnight. The resulting solid was 35 recovered by decantation, washed with cold hexane and O O) dried under reduced pressure to give 2.97 g of 1-(5,6- \ & dimethoxy-1H-inden-3-yl)pyrrolidine. Yield was 46 per HCSi T cent. fy \ / No "H NMR (CD) & 1.60 (m, 4H), 3.26 (m, 4H), 3.29 (s. N NN 2H), 3.51 (s, 3H), 3.59 (s, 3H), 5.05 (s, 1H), 6.85 (s, 1H), HC- 7. Me 2 Me 7.25 (s, 1H). C{H} NMR (CD) & 25.39, 35.73, 50.24, HC CH 55.67, 56.49, 99.27, 106.85, 109.59, 135.48, 138.70, 148.63, 148.90, 150.61. GC-MS: Calcd for CHNO: 245.14, 45 found 245.15. To a solution of 0.079 g of (1-((1,2,3,3a,7a-m)-5- Step 2 Preparation of (5,6-Dimethoxy-3-(1-pyrrolidino)-1H methoxy-3-pyrrollidinyl-1H-inden-1-yl)-N-(1,1- inden-1-yl)lithium dimethylethyl)-1,1-dimethylsilanaminato(2-)-N) ((2- (dimethylamino-N)phenyl)methyl-C)titanium in about 10 mL of EtO was added 0.732 g of PbCl. The reaction 50 mixture was stirred for several days. The solvent was N removed and the residue was extracted with hexane, then MeO filtered and the product was isolated by removal of the solvents under reduced pressure. NMR spectra showed the presence of two isomerS along with a very Small amount of 55 the (chloro) (cyclopentadienyl) complex. MeO Li "H (CD) 8 0.67, 0.70, 0.73, 0.84, 1.28, 1.35, 1.40, 1.61, 1.62, 2.1, 2.15, 2.20, 2.29, 2.44, 2.47, 2.58, 2.60, 2.83, 3.22, 3.46, 3.63, 5.15, 5.64, 5.78, 6.35, 6.6-6.78, 6.83–7.0, 7.32, 60 1-(5,6-Dimethoxy-1H-inden-3-yl)pyrrollidine (2.87 g, 7.37, 7.78, 7.82. C (CD) & 158.5, 156.3, 1541, 153.1, 11.7 mmol) was dissolved in a mixture of 40 mL of toluene 151.1, 149.5, 147.2, 143.3, 131.6, 130.4, 129.4, 127.7, and 40 mL of hexane then 7.0 mL of 1.6 M n-BuLi was 126.6, 126.4, 125.9, 123.6, 123.4, 122.7, 121.6, 120.1, added dropwise via Syringe over a 5 min period. The 118.4, 118.1, 117.5, 116.6, 115.2, 107.9, 102.7, 101.7, 101.4, reaction mixture was stirred for 3 hrs. After this time, the 100.3, 98.7, 97.1, 89.2, 72.1, 69.5, 55.3, 54.1, 50.8, 50.1, 65 Solid was filtered, washed with 30 mL of toluene and then 47.5, 45.3, 35.1, 33.2, 32.1, 30.3, 25.8, 25.4, 24.4, 23.2, 21.0, with 60 mL of hexane and dried in vacuum to afford the 14.5, 4.5, 3.2, 2.6., 1.4. desired product as a yellow solid. (2.67 g, 95 percent yield). US 6,555,634 B1 25 26 Step 3 Preparation of 1-(5,6-Dimethoxy-3-(1-pyrrolidino)- Step 5 Preparation of Dichloro(1-((1,2,3,3a,7a-m)-5,6- 1H-inden-1-yl)-N-(1,1-dimethylethyl)-1,1- dimethoxy-3-(1-pyrrolidino)-1H-inden-1-yl)-N-(1,1- dimethylsilanamine dimethylethyl)-1,1-dimethylsilanaminato(2-)-N)titanium CH / O N MeO 1O

MeO -CH HC1 V HCSi TIC HN-t-Bu 15 fy \ / N (5,6-Dimethoxy-3-(1-pyrrolidino)-1H-inden-1-yl)lithium HC-7( (2.67 g, 10.63 mmol) was slurried in 100 mL of THF then HC CH added to a solution of N-(tert-butyl)-N-(1-chloro-1,1- 3.557 g (9.6 mmol) Of TiCls.(THF) were suspended in dimethylsilyl)amine (2.73 g, 16.47 mmol) in 150 mL of THF 70 mL of THF. To this solution, 3.71 g (9.6 mmol) of over a 25 min period, with stirring continued for 20 h. The (1-(((1,1-dimethylethyl)amino)dimethylsilyl)-5,6- Solution was evaporated in vacuum to give a dark red oil. dimethoxy-3-(1-pyrrolidino)-1H-inden-1-yl)cilithium salt The oil was extracted hexane (40 mL), filtered, and the Slurried in 40 mL of THF were added within 5 min. The 25 solution was stirred for 50 minutes, then 1.735 g of PbCl. Solvent was removed under vacuum to give 3.83 g of (6.24 mmol) were added and the solution was stirred for 50 1-(5,6-dimethoxy-3-(1-pyrrolidinyl)-1H-inden-1-yl)-N-(1, min. THF was then removed under reduced pressure. The 1-dimethylethyl)-1,1-dimethylsilanamine as a dark red oil in residue was then extracted with 120 mL of toluene, the 96 percent yield. resulting Solution was filtered, and the toluene was removed under reduced pressure. The residue was then triturated with 60 mL of hexane and the precipitate was collected via H NMR (CD) 8 -0.07 (s, 3H), 0.16 (s, 3H), 0.57 (s, filtration on a frit, washed with 60 mL of hexane and dried 1H), 1.13 (s, 9H), 1.66 (m, 4H), 3.28 (m, 4H), 3.38 (d. 1H, under vacuum to yield 3.25 g of the crude product as a J–1.7 Hz), 3.60 (s, 3H), 3.65 (s, 3H), 5.34 (d. 1H, dark-green solid. Yield was 69 percent. The complex was J-1.7 Hz), 7.20 (s, 1H), 7.29 (s, 1H). 'C{H} NMR 35 recrystallized from a toluene/hexane mixture at -27 C. to (CD) 8 -1.49, 0.61, 25.24, 34.00, 43.13, 49.48, 50.73, give highly pure dichloro(1-((1,2,3,3a,7a-m)-5,6-dimethoxy 3-(1-pyrrolidino)-1H-inden-1-yl)-N-(1,1-dimethylethyl)-1, 56.06, 56.31, 103.58, 106.14, 108.93, 134.57, 139.92, 1-dimethylsilanaminato(2-)-N)titanium. 148.11, 148.28, 149.48. H NMR (CDC1) & 0.65 (s, 3H), 0.82 (s, 3H), 1.29 (s. 9H), 2.04 (m, 4H), 3.68 (m, 2H), 3.81 (s, 3H), 3.91 (s, 3H), Step 4 Preparation of (1-(((1,1-Dimethylethyl)amino) 40 3.98 (m, 2H), 5.54 (s, 1H), 6.77 (s, 1H), 7.10 (s, 1H) dimethylsilyl)-5,6-dimethoxy-3-(1-pyrrolidino)-1H-inden 'C{H} NMR (CDC1) & 1.50, 3.74, 26.10, 32.88, 50.83, 1-yl)cilithium Salt 56.00, 56.26, 60.73, 92.56, 103.79, 106.83, 106.02, 122.29, 132.17, 149.43, 152.70, 153.26. EXAMPLE 8 45 Preparation of (1-((1,2,3,3a,7a-m)-5,6-Dimethoxy-3- (1-pyrrolidino)-1H-inden-1-yl)-N-(1,1- C dimethylethyl)-1,1-dimethylsilanaminato(2-)-N) MeO dimethyltitanium

50 CH / MeO -CH3 O Li Si c1 V LN-t-Bu 55 3.68 g (9.82 mmol) of 1-(5,6-dimethoxy-3-(1- pyrrolidino)-1H-inden-1-yl)-N-(1,1-dimethylethyl)-1,1- HCyS Y CH3 dimethylsilanamine were combined with a mixture of 60 mL HC CH of hexane and 30 mL of toluene. To this solution 12.3 mL 60 \/ (19.6 mmol) of n-BuLi (1.6 M) were added dropwise. The solution was stirred for 7 h at room temperature. The resulting precipitate was collected via filtration, washed with HC-7(HC CH 60 mL of hexane and then dried under reduced pressure to 65 give 3.71 g of the dilithium salt as a yellow solid. Yield was 0.3 g (0.61 mmol) of dichloro(1-(1,2,3,3a,7a-m)-5,6- 98 percent. dimethoxy-3-(1-pyrrollidinyl)-1H-inden-1-yl)-N-(1,1- US 6,555,634 B1 27 28 dimethylethyl)-1,1-dimethylsilanaminato(2-)-N) titanium became brown/orange in color. Next, 800 mL of water were were partly dissolved in 50 mL of EtO. While stirring the added to the reaction mixture, and the product was extracted solution, 0.85 mL (1.28 mmol) of MeLi (1.5 M) were added with diethyl ether. The ether layer was washed with 400 mL dropwise over a 5 minute period. The Solution changed color of a saturated NaCl solution and dried over MgSO. After from black to dark red. The Solution was stirred for an removal of the ether, the dark brown/orange oil was distilled additional 2 hrs. The solvent was removed under reduced to yield a light yellow Solid weighing 12.0 g, 80.6 percent. pressure and the residue was extracted with hexane (3x40 mL), then filtered. The filtrate was evaporated to dryness "H NMR (CD): & 1.09 (d. 3H, J =7.44 Hz), under reduced pressure to give 0.147 g (53 percent yield) of 2.05-2.11 (dd, 1H, J-3.42 Hz, J-16.8 Hz), 2.33 (m, the desired product as a dark red crystalline Solid. 1H), 2.66-2.71 (dd, 1H, J =7.68, J =16.8 Hz), 5.39 "H NMR (CD): 8 0.19 (s.3H), 0.54 (s.3H), 0.69 (s.3H), (s, 2H), 6.38 (s, 1H), 7.12 (s, 1H). C{H} NMR (CD): 0.77 (s, 3H), 1.56 (s, 9H), 1.59 (m, 4H), 3.34 (m, 2H), 3.36 8 16.46, 34.74, 42.39, 102.13, 102.44, 105.68, 131.37, (s.3H), 3.50 (s.3H), 3.51 (m, 2H), 5.42 (s, 1H), 6.76 (s, 1H), 148.49, 150.35, 154.13, 205.60 GC-MS: Calcd. for 7.09 (s, 1H). C{H} (CD): 8 2.41, 4.76, 25.99, 34.76, CHOs: 190.06, found 190.05. 47.83, 50.49 52.51, 55.07, 55.62, 57.51, 82.52, 103, 44, 15 Step 3 Preparation of 1,3-Dioxol-5-hydroxyl-6-methyl-2.5, 103.81, 106.12, 119, 63, 129.79, 143.61, 151.45, 151.65. 6,7H-S-indacene EXAMPLE 9 OH Preparation of Dichloro(N-(1,1-dimethylethyl)-1,1- dimethyl-5-((4a,5,6,7,7a-m)-6-methyl-5H-indeno(5, O 6-d)-1,3-dioxol-5-yl)silanaminato(2-)-N) titanium { CH Step 1 Preparation of 1,3-Dioxol-5-(N,N-dimethylamino)- O 6-methyl-2.5H-s-indacene

25 In a 250 mL round bottom flask, 2.438 g (64.45 mmol) of NMe2 Sodium borohydride were stirred in about 150 mL of anhy drous ethanol. To this stirring solution, 12.01 g (63.19 mmol) of 1,3-dioxol-6-methyl-2,5,6,7H-s-indacene-5-one { O CH was added and the Solution was stirred overnight at room temperature. Water was added (200 mL) to the reaction Phosphorus oxychloride (23.2 mL, 0.249 moles) was mixture and stirred about 10 minutes. The Solution was then added dropwise by Syringe while Stirring to dimethylforma extracted with ethyl acetate (3x200 mL). The ethyl acetate mide (98 mL, 1.264 moles) in an ice bath under argon for layer was further washed twice with about 200 mL each about 20 minutes. IsoSafrole (30.0 mL, 0.207 moles) was portion and then dried with MgSO. Ethyl acetate was then added dropwise by addition funnel to this stirring Solution. 35 removed under reduced pressure resulting in the isolation of After addition was completed, the reaction mixture was 10.65 g of the desired product as a white solid. Yield was heated to 110° C. for three hours. The reaction mixture was 87.7 percent. then poured into 800 mL of ice, washed with three 300 mL GC-MS: Calcd for CHOs: 192.08, found 192.05. portions of diethyl ether, and the aqueous layer was made basic (pH=8) by the addition of 10 percent aqueous NaOH 40 (about 40 g NaOH in 400 mL of water). The desired product was then extracted with four 300 mL portions of ether and the combined organic extracts were dried over MgSO. The CO ether was removed under reduced pressure leaving a 45 medium brown solid. The product was recrystallized from In a 250 mL round bottom flask 6.00 g (31.2 mmol) of hexane to give 17.0 g of a light yellow solid. Yield was 51.8 1,3-dioxol-5-hydroxyl-6-methyl-2,5,6,7H-s-indacene was percent. dissolved in 100 mL of anhydrous dimethylsulfoxide "H NMR (CD): 8 1.91 (s, 3H); 2.18 (s, 6H); 3.79 (s, (DMSO) and the mixture was refluxed for about 5 hours. 1H); 5.42 (s, 1H); 5.44 (s, 1H); 6.04 (s, 1H); 6.65 (s, 1H); The solution was poured into 250 mL of ice, then extracted 7.04 (s, 1H). C{H} NMR (CD): 8 40.92, 74.08, 100.83, 50 with diethyl ether (3x200 mL). The combined organic 101.96, 106.73, 127.25, 137.39, 138.62, 145.39, 147.09, fractions were dried over MgSO. The ether was removed 147.55. under reduced pressure leaving a light tan/orange Solid. This Step 2 Preparation of 1,3-Dioxol-6-methyl-2,5,6,7H-s- product was recrystallized from cold hexane yielding 4.15g indacene-5-one 55 of highly pure product. 'C {H} NMR (CD): & 16.48, 42.45, 100.70, 101.45, 105.38, 127.35, 137.05, 140.02, 144.32, 145.42, 147.01. O Step 5 Preparation of (3,5-Dioxol-8-methyl-1,4H-s- CH indacene-1-yl)lithium 60 O O In a 2L flask, 400 mL of ethanol and 400 mL of water were combined and stirred with 36 g of NaOH (0.900 COO moles). To this mixture, 17.00 g (0.078 moles) of 1,3-dioxol 65 Li 5-(N,N-dimethylamino)-6-methyl-2,5H-s-indacene were added and the mixture was stirred overnight. The Solution US 6,555,634 B1 29 30 1,3-dioxol-6-methyl-2.5H-s-indacene (4.150 g, 23.8 Step 8 Preparation of Dichloro(N-(1,1-dimethylethyl)-1,1- mmol) was dissolved in 150 mL of hexane and 14.9 mL of dimethyl-((4a,5,6,7,7a-m)-6-methyl-5H-indeno(5,6-d)-1,3- 1.6 M n-BuLi were added dropwise via syringe over a 15 dioxol-5-yl)silanaminato(2-)-N)titanium min period. The reaction mixture was stirred for 20 h. After this time the Solid was filtered, washed with 60 mL of 5 ? O hexane and allowed to dry in vacuum to afford the desired product as an off-white solid (3.64 g) in 85 percent yield. Step 6 Preparation of (N-(1,1-Dimethylethyl)amino)(3,5- dioxol-8-methyl-1,4H-s-indacene-1-yl)dimethylsilane C. ": III.S.V /"S... III 15 HC-7(N HC CH Si -CH3 HC1 V HN-t-Bu 0.924 g (2.92 mmol) of (5-(((1,1-dimethylethyl)amino) dimethylsilyl)-5H-6-methyl-indeno(5,6-d)-1,3-dioxol-5-yl) lithium, lithium salt were added to a slurry of 1.08 g (2.92 mmol) of TiCls.(THF). In THF. The reaction product was stirred about one 5 hour, then 0.528 g (1.90 mmol) of PbCl. were added and the mixture was stirred another hour. The In a 250 mL round bottom flask, 2.76 g (16.65 mmol) of 25 Volatile components were then removed under reduced N-(tert-butyl)-N-(1-chloro-1,1-dimethylsilyl)amine were preSSure and the residue was extracted with toluene. After stirred in about 75 mL of THF. The Solution was stirred filtration, the Volatile components were removed under while 2.00 g (11.10 mmol) of 3,5-dioxol-8-methyl-1,4H-s- reduced pressure. Solids were collected on a frit, and washed with hexane to yield a dark red/brown solid that was dried indacene-1-yl)lithium in about 20 mL THF were added under vacuum. Recrystallization of the product gave 450 mg dropwise. The reaction mixture was stirred overnight. The of highly pure complex. Volatile components were removed under reduced pressure "H NMR (CD): 8 0.40 (s.3H), 0.44 (s, 3H), 1.34 (s, 9H), and the residue was extracted with hexane. After filtration, 2.11 (s, 3H), 5.14 (s, 1H), 5.16 (s, 1H), 6.54 (s, 1H), 6.55 (s, the volatile components were removed under Vacuum leav 1H), 7.00 (s, 1H). C {H} NMR (CD): 8 4.89, 5.00, ing a light brown/green oil weighing 3.14 g, 92.9 percent 35 19.52, 32.46, 62.09, 93.39, 101.20, 101.61, 102.94, 121.58, yield. 132.54, 133.88, 143.97, 151.57, 151.87. EXAMPLE 10 Preparation of (N-(1,1-Dimethylethyl-1,1-dimethyl 'C{H} NMR (CD): 8 0.29, 0.82, 1.11, 1.20, 18.19, 5-((4a,5,6,7,7a-m)-6-methyl-5H-indeno(5,6-d)-1,3- 33.85, 49.54, 51.12, 100.60, 100.72, 100.95, 105.08, 125.90, 40 dioxol-5-yl)silanaminato(2-)-N)dimethyltitanium 139.06, 139.41, 144.75, 146.22. Step 7 Preparation of (5-(((1,1-Dimethylethyl)amino) dimethylsilyl)-5H-6-methyl-indeno(5,6-d)-1,3-dioxol-5-yl) 45 lithium, Lithium Salt

CO 50 Li Ey V /"SF -CH3 N Si HC1 LN-t-Bu\ 55 HC –7( HC CH

0.30 g (0.72 mmol) of dichloro(N-(1,1-dimethylethyl)-1, In a 100 mL round bottom flask, 3.14 g (10.3 mmol) of 1-dimethyl-5-((4a,5,6,7,7a-m)-6-methyl-5H-indeno(5,6-d)- (N-(1,1-dimethylethyl)amino)(3,5-dioxol-8-methyl-1,4H-s- 60 1,3-dioxol-5-yl)silanaminato(2-)-N)titanium were dissolved indacene-1-yl)dimethylsilane were stirred in about 75 mL of in 30 mL of EtO. To this solution, 0.52 mL (1.57 mmol) of MeMgI (3.0 M) were added dropwise over a 5 minute hexane. To this stirring solution 8.26 mL (20.6 mmol) of 2.5 period. The Solution changed color from brown-red to Mn-BuLi were added dropwise by syringe. After stirring for green-yellow. After the addition of MeMgI was completed, 3 days, the resulting precipitate was filtered, washed with 65 the solution was stirred for 60 minutes. The EtO was hexane, and dried under vacuum to give a light tan Solid removed under reduced pressure and the residue was weighing 3.51 g. extracted with hexane (2x20 mL), the solution was filtered, US 6,555,634 B1 31 32 and the filtrate was evaporated to dryneSS under reduced Step 3 Preparation of (7-(Dimethylamino)-5-(((1,1- pressure to give 0.168 g of the desired product (62 percent dimethylethyl)amino)dimethylsilyl)-6-methyl-5H-indeno(5, yield) as a yellow Solid. 6-d)-1,3-dioxol-5-yl)lithium, Lithium Salt

'C{H} (CD) & 5.72, 5.80, 18.52,3441, 50.59, 54.92, 5 NMe2 57.88, 89.42, 100.81, 100.89, 103.38, 115.83, 130.69, O 140.08, 149.33, 149.68. COC)—aO EXAMPLE 11 1O Li HC- Si Preparation of Dichloro(N-(1,1-dimethylethyl)-1,1- / YOH, dimethyl-5-((4a,5,6,7,7a-m)-5-(N,N-dimethylamino)- 6-methyl-5H-indeno(5,6-d)-1,3-dioxol-5-yl) Silanaminato(2-)-N)titanium 15 Step 1 Preparation of (7-(Dimethylamino)-6-methyl-5H In a 250 mL round bottom flask, 3.035 g (8.76 mmol) indeno(5,6-d)-1,3-dioxol-5-yl)lithium 1-(7-(dimethylamino)-6-methyl-5H-indeno(5,6-d)-1,3- dioxol-5-yl)-N-(1,1-dimethylethyl)silanamine was stirred in NMe2 about 100 mL of hexane. 7.0 mL of 2.5 M n-BuLi (17.52 O mmol) were added by Syringe and the reaction mixture was stirred overnight. The solids were then filtered off, washed with excess hexane and dried under vacuum to give 3.23g COC)—aO 25 of product. Li Step 4 Preparation of Dichloro(1-((4a,5,6,7,7a-m)-7- In a 250 mL round bottom flask, 6.347 g (29.91 mmol) of (dimethylamino)-6-methyl-5H-indeno(5,6-d)-1,3-dioxol-5- (7-(N,N-dimethylamino)-6-methyl-5H-indeno(5,6-d)-1,3- yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanaminato(2-)-N) dioxol-5-yl)lithium were stirred in 20 mL of toluene. After titanium. adding 100 mL of hexane to this stirring solution, 12.0 mL of 2.5 M n-BuLi (29.91 mmol) were added slowly by Syringe and the reaction mixture was stirred overnight. The ? O solids were filtered off and dried under vacuum to give 5.404 g (80.9 percent yield) of the desired product. 35 Step 2 Preparation of (N-(1,1-Dimethylethyl)amino)(3,5- dioxol-7-(N,N-dimethylamino)-8-methyl-1,4H-s-indacene C. NMe2 1-yl)climethylsilane 40 III S. . . . NMe2 "...tv /"S N

{ OC) CH 45 HC-7(HC CH

In a drybox 1.031 g (2.78 mmol) of TiCl(THF) were 50 suspended in about 50 mL of THF in a 100 mL round bottom In a 100 mL round bottom flask, 2.02 mL (12.11 mmol) flask. 1.000 g of (2.78 mmol) (7-(dimethylamino)-5-(((1,1- of N-(tert-butyl)-N-(1-chloro-1,1-dimethylsilyl)amine were dimethylethyl)amino)dimethylsilyl)-6-methyl-5H-indeno(5, stirred in about 50 mL of THF. A solution of (7- 6-d)-1,3-dioxol-5-yl)lithium, lithium salt was added as a (dimethylamino)-6-methyl-5H-indeno(5,6-d)-1,3-dioxol-5- Solid and the reaction mixture was stirred for 1 % h. 0.503 yl)lithium (1.802g, 8.07 mmol) dissolved in about 10 mL of 55 g (1.81 mmol) Of PbCl was then added and stirring was THF was added dropwise. After stirring overnight, the continued for another hour. Solvent was then removed under Volatile components were removed under reduced pressure. reduced preSSure. The residue was extracted with toluene, The remaining Solids were washed with hexane and filtered. the Solution was filtered and the solvent was removed under The volatile components were removed from the filtrate reduced preSSure. The residue was extracted with hexane leaving the product as an orange/brown oil weighing 2.82 g. 60 and filtered. The volatile components were removed under H NMR (CD): 8 0.03 (s, 3H); 0.01 (s, 3H); 1.03 (s, reduced pressure leaving the desired product as a brown/ 9H); 2.13 (s, 3H); 2.76 (s, 6H); 2.99 (s, 1H); 5.47 (s, 1H); black Solid. 5.50 (s, 1H); 7.09 (s, 1H); 7.16 (s, 1H), '{H} NMR (CD): 8 0.20, 0.27, 0.60, 15.51, 33.65, 33.79, 43.36, 48.27, 65 C{H} NMR (CD): 883, 56.00, 56.26, 60.73, 92.56, 49.13, 49. 41, 100.46, 100.58, 105.21, 132.06, 137.37, 103.79, 106.83, 107.02, 122.29, 132.17, 149.43, 152.70, 137.51,144.73, 145.94. 153.26. US 6,555,634 B1 33 34 EXAMPLE 12 Step 2 Preparation of 1-(5,6-Dimethoxy-1H-inden-1-yl)-N- (1,1-dimethylethyl)-1,1-dimethylsilanamine Preparation of (1-((4a,5,6,7,7a-m)-7- MeO (Dimethylamino)-6-methyl-5H-indeno(5,6-d)-1,3- 5 dioxol-5-yl)-N-(1,1-dimethylethyl)-1,1- dimethylsilanaminato(2-)-N)dimethyltitanium MeO -CH3 Si HC1 V HN-t-Bu ? O 1O (5,6-Dimethoxy-1H-inden-1-yl)lithium (2.5 g., 13.73 mmol) slurried in 40 mL of THF was added to a solution of N-(tert-butyl)-N-(1-chloro-1,1-dimethylsilyl)amine (3.185 g, 19.22 mmol) in 100 mL of THF over a 25 min period. C. NMe2 After stirring for 18 h, the volatile components were removed under reduced pressure. The residue Solution was extracted with hexane (40 mL). After filtration the volatile HCity. Si TiCH components were removed in under vacuum to give 3.95 g, fy \ / You, 94 percent yield of the desired product as a light yellow oil. N H (CD) 8 -0.12 (s.3H), 0.00 (s, 3H), 0.53 (s, 1H), 1.09 S. 9H), 3.46 (s.1H), 3.54 (s.3H), 3.64 (s.3H), 6.55 (dd, 1H, HC-7( J.--5.2 Hz, J-1.7 Hz), 6.85 (d. 1H), J =4.2 Hz), HC CH 6.92 (s, 1H), 7.16 (s, 1H). C{H} (CD) 8 -1.36, 0.18, 33.90, 48.66, 49.53, 55.85, 56.27, 105.45, 108.68, 129.20, 134.53, 137.96, 138.22, 148.02, 148.95. 25 Step 3 Preparation of 1-(((1,1-Dimethylethyl)amino) Dichloro(1-((4a,5,6,7,7a-m)-7-(dimethylamino)-6- dimethylsilyl)-5,6-dimethoxy-1H-inden-1-yl)lithium, methyl-5H-indeno(5,6-d)-1,3-dioxol-5-yl)-N-(1,1- Lithium Salt. dimethylethyl)-1,1-dimethylsilanaminato(2-)-N) titanium MeO (0.5 mmol) was dissolved in 30 mL of EtO. To this solution, MeMgI (1.0 mmol) was added dropwise over a 5 minute period. After addition of MeMgI was completed, the solu C Li tion was stirred for 60 minutes. EtO was removed under MeO -CH HC1 V reduced preSSure and the residue was extracted with hexane 35 LN-t-Bu (2x20 mL), the solution was filtered, and the filtrate was evaporated to dryneSS under reduced pressure to give the 3.80 g (12.44 mmol) Of 1-(5,6-dimethoxy-1H-inden-1- product as a yellow Solid. yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamine were combined with 100 mL of hexane. To this solution, 15.55 40 mL (24.88 mmol) of n-BuLi (1.6 M) were added dropwise. EXAMPLE 13 The solution was then stirred for 8 h at room temperature. The resulting precipitate was collected via filtration, washed with 60 mL of hexane, then dried under reduced pressure to Preparation of Dichloro(1-((1,2,3,3a,7a-m)-5,6- give 3.95 g of the desired product as a pink colored Solid. dimethoxy-1H-inden-1-yl-N-(1,1-dimethylethyl)-1, Yield was 99 percent. Step 4 Preparation of Dichloro(1-((1,2,3,3a,7a-m)-5,6- 1-dimethylsilanaminato(2-)-N) titanium dimethoxy-1H-inden-1-yl)-N-(1,1-dimethylethyl)-1,1- dimethylsilanaminato(2-)-N)titanium. Step 1 Preparation of (5,6-Dimethoxy-1H-inden-1-yl) lithium. 50

MeO

MeO 55 Li HCyS 5,6-Dimethoxy-indene (4.82 g, 27.35 mmol) was dis 60 Solved in a mixture of 20 mL of toluene and 180 mL of ii. 1 V/N hexane and 16.25 mL of 1.6 Mn-BuLi were added dropwise via a Syringe over a 5 min period forming a white precipitate. HC-7( The reaction mixture was stirred for 4 h then filtered. The HC CH solids were washed with 60 mL of hexane and allowed to dry 65 under reduced preSSure to afford the desired anion as a light 4.58 g (12.4 mmol) Of TiCls.(THF) were suspended in pink Solid (4.62 g, 98 percent yield). 90 mL of THF. To this slurry 3.92 g (12.4 mmol) of US 6,555,634 B1 35 36 1-(((1,1-dimethylethyl)amino) dimethylsilyl)-5,6- EXAMPLE 1.5 dimethoxy-1H-inden-1-yl)lithium, lithium salt dissolved in 40 mL of THF was added within 5 min. After stirring for 50 minutes, 2.23 g of PbCl (8.0 mmol) were added and the Step 1 Preparation of 5,6-Dimethoxy-3-phenyl-1H-indene Solution was stirred for 50 min. The THF was then removed under reduced pressure. The residue was dissolved in 70 mL of toluene and Solution was filtered. Toluene was removed under reduced preSSure leaving a Sticky brown residue. The residue was triturated with 80 mL of hexane, resulting in the formation of light brown-yellow solid. The solid was col MeO lected on a frit, washed with 30 mL of hexane and dried under reduced pressure to give 3.45 g of crude product. The complex was later crystallized from a toluene/hexane mix MeO ture at -27 C. to give 1.16 g of the pure product. Yield was 15 22 percent. The proton NMR shows that the complex and toluene crystallize in a ratio of 1:1. 2,3-Dihydro-5,6-dimethoxy-3-phenyl-1H-inden-1-one "H (CDC1) & 0.41, (s, 3H), 0.62 (s, 3H), 1.37 (s, 9H), (8.010g, 29.85 mmol) and NaBH (1.355 g, 35.82 mmol) 3.30 (s, 3H), 3,34 (s, 3H), 6.24 (d. 1H, J =3.2 Hz), 6.51 were stirred in diethylether (100 mL) at 0° C. as ethanol (100 (s, 1H), 6.77 (s, 1H), 6.93 (d. 1H, J =3.2 Hz). "C{H} mL) was added slowly. The mixture was allowed to stir at (CDC1) & 0.91, 3.31, 32.47, 55.26, 55.59, 62.28, 97.30, room temperature for 24 hours. The mixture was then 103.29, 104.69, 119.01, 127.29, 131.78, 132.75, 15422, poured onto crushed ice and then washed with diethylether 155.06. (3x100 mL). The organic fractions were then dried over 25 MgSO, filtered, and the volatile components were removed EXAMPLE 1.4 under Vacuum resulting in the isolation of a yellow Solid. This solid was refluxed in anhydrous DMSO (150 mL) for Preparation of (1-((1,2,3,3a,7a-m)-5,6-Dimethoxy 5 hours and then cooled to room temperature. The mixture 1H-inden-1-yl)-N-(1,1-dimethylethyl)-1,1- was poured onto crushed ice and the total Volume was dimethylsilanaminato(2-)-N)dimethyltitanium diluted to 500 mL using HO. This mixture was then washed using diethylether (5x100 mL). The organic fractions were then combined, washed with HO (1x100 mL) and then dried over MgSO. The mixture was filtered and the volatile components were removed resulting in the isolation of a 35 dark red oil. Chromatography of the oil on Silica gel using hexane/CHCl (1/1 vol) as the diluent resulted in the isolation of the 5,6-dimethoxy-3-phenyl-1H-indene as a yellow microcrystalline solid (4.91 g, 65.2 percent yield).

40 HCSi TinCH H NMR (CD): 83.17 (s, 2H), 3.43 (s.3H), 3.53 (s.3H), HC \ / CH 6.3 (m, 1H), 6.88 (s, 1H), 7.1-7.1 (m, 1H), 7.22 (s, 1H), 7.29 N (t, J =7.2 Hz, 2H), 7.63 (d, J =7.4 Hz, 2H). C{H} NMR (CD): 838.18, 55.98, 56.13, 105.61, 109.59,127.69, HC-7( 45 HC CH 128.97, 129.46, 137.19, 137.66, 145.79, 148.94, 149.60. Step 2 Preparation of (5,6-Dimethoxy-3-phenyl-1H-inden 0.19 g (1.42 mmol) of dichloro(1-((1,2,3,3a,7a-m)-5,6- 1-yl)lithium. dimethoxy-1H-inden-1-yl)-N-(1,1-dimethylethyl)-1,1- 50 dimethylsilanaminato(2-)-N) titanium were partially dis solved in 50 mL of EtO. To this solution, 0.63 mL (0.94 mmol) of MeLi (1.5 M) were added dropwise over a 5 minute period. The Solution changed color from brown to MeO yellow. The solution was stirred for an additional 60 55 minutes, then the Et2O was removed under reduced preSSure and the residue was extracted with hexane (2x20 mL). The Solution was filtered and the filtrate was evaporated to MeO dryness under reduced pressure to give 0.100 g (58 percent Li yield) of the desired product as a yellow solid. 60 "H NMR (CD): 8 -0.02 (s, 3H), 0.43 (s, 3H), 0.59 (s. 3H), 0.85 (s, 3H), 1.51 (s, 9H), 3.32 (s, 3H), 3.39 (s, 3H), 5,6-dimethoxy-3-phenyl-1H-indene (1.26 g, 4.99 mmol) 6.04 (d. 1H, J =2.8), 6.69 (s, 1H), 6.73 (s, 1H), 6.98 (d, was dissolved in a mixture of 15 mL of toluene and 25 mL 1H, J, -2.7). 'C{H} NMR (CD): 8 2.01, 4.15,34.50, 65 of hexane and 3.06 mL of 1.6 M n-BuLi were added 52.35, 55.20, 55.47, 58.22, 90.95, 103.27, 105.38, 113.49, dropwise Via Syringe over a 3 min period. The Solution 125.14, 128.90, 129.07, 152.14, 153.09. developed a yellow-light green precipitate during addition of US 6,555,634 B1 37 38 n-BuLi. The reaction mixture was stirred for 3 h and then Step 5 Preparation of Dichloro(1-((1,2,3,3a,7a-m)-5,6- filtered, washed with 60 mL of hexane and dried in vacuum dimethoxy-3-phenyl-1H-inde n-1-yl)-N-(1,1- to afford the desired product as a yellow solid (1.24 g) in 98 dimethylethyl)-1,1-dimethylsilanaminato(2-)-N)titanium. percent yield. /CH Step 3 Preparation of 1-(5,6-Dimethoxy-3-phenyl-1H O inden-1-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamine 1O OO

MeO V HCIS3 y TCI'N, 15 ii. 1 V/ N MeO -CH HC1 V HC-7( HN-t-Bu HC CH 1.61 g (4.4 mmol) Of TiCls.(THF) were suspended in 40 mL of THF. To this solution, 1.71 g (4.4 mmol) of (1-(((1, (5,6-dimethoxy-3-phenyl-1H-inden-1-yl)lithium (1.24 g, 1-dimethylethyl)amino)dimethylsilyl)-5,6-dimethoxy-3- 4.8 mmol) was dissolved in 20 mL of THF and added to a 25 phenyl-1H-inden-1-yl)lithium, lithium salt dissolved in 30 solution of N-(tert-butyl)-N-(1-chloro-1,1-dimethylsilyl) mL of THF were added within 5 min. The Solution was then amine (1.035g., 6.24 mmol) in 50 mL of THF over a 25 min stirred for 50 minutes, after which 0.79 g of PbCl (2.8 period, with stirring continued for 20 h. The solution was mmol) were added. After stirring for an additional 50 then evaporated under reduced pressure and the residue was minutes, THF was removed under reduced pressure. The extracted with hexane (50 mL). After filtration, the solvent residue was dissolved in 50 mL of toluene and the Solution was removed under reduced pressure. To this residue, 30 mL was filtered. Toluene was removed under reduced preSSure of hexane was added and the flask was put aside into a leaving a red Solid. The product was recrystallized from freezer (-27° C) for 2 days. After that time the crystallized warm hexane and dried under reduced pressure to give 0.367 solid was filtered off and the solvent was removed leaving 35 g, 17 percent, of highly pure product. 1.68 of the product as a yellow oil. H NMR (CDC1) & 0.51 (s, 3H), 0.69 (s.3H), 1.39 (s. 9H), 3.28 (s, 3H), 3.33 (s, 3H), 6.59 (s, 1H), 6.87 (s, 1H), Step 4 Preparation of (1-(((1,1-Dimethylethyl)amino) 7.08 (s, 1H), 7.16 (t, 1H, J =7.7 Hz), 7.29 (t, 2H), dimethylsilyl)-5,6-dimethoxy-3-phenyl-1H-inden-1-yl) J-7.4 Hz), 7.74 (d. 2H, J =7.5 Hz). "C{H} NMR lithium, Lithium Salt. 40 (CDC1) & 0.96, 3.58, 32.64, 55.28, 55.39, 62.59, 97.82, 101.94, 105.37, 124.90, 128.72, 128.97, 129.35, 131.05, 132.67, 135.22, 135.88, 153.93, 155.67.

45 EXAMPLE 16

MeO Preparation of (1-((1,2,3,3a,7a-m)-5,6-Dimethoxy-3- phenyl-1H-inden-1-yl)-N-(1,1-dimethylethyl)-1,1- dimethylsilanaminato(2-)-N)dimethyltitanium 50 MeO O Li-CH3 Si HC1 LN-t-Bu\

55

1.68 g (4.4 mmol) of 1-(5,6-dimethoxy-3-phenyl-1H inden-1-yl)-N-(1,1-dimethylethyl)-1,1-dimethylsilanamine were combined with 50 mL of hexane. To this solution, 5.5 60 iii. S. mL (8.8 mmol) of n-BuLi (1.6 M) were added dropwise ''', 7"s." resulting in immediate formation of a precipitate. After N Stirring for 7 hat room temperature, the resulting precipitate HC-7( was collected via filtration, washed with 40 mL of hexane 65 HC CH and then dried under reduced preSSure to give 1.71 g of the product as a yellow solid. Yield was 99 percent. US 6,555,634 B1 39 40 Dichloro(1-((1,2,3,3a,7a-m)-5,6-dimethoxy-3-phenyl What is claimed is: 1H-inden-1-yl)-N-(1,1-dimethylethyl)-1,1- 1. A metal complexes corresponding to the formula: dimethylsilanaminato(2-)-N)titanium (0.107 g., 0.210 mmol) was stirred in diethylether (50 mL) while MeMgBr (0.430 A mmol, 0.306 mL of 3.0 M solution in diethylether) was 5 R RA added dropwise. This mixture was then allowed to stir for 30 RA minutes. After the reaction period the Volatiles were removed and the residue was extracted and filtered using hexane. Removal of the hexane under vacuum resulted in the 1O isolation of the desired product as a yellow residue which solidified upon standing. Yield was 0.031 g, 31.7 percent.

H NMR (CD): 8 0.19 (s.3H), 0.49 (s.3H), 0.66 (s.3H), 15 0.71 (s.3H), 1.51 (s, 9H), 3.34 (s, 3H), 3.36 (s, 3H), 6.35 (s, where M is a metal from Group 4 of the Periodic Table of 1H), 6.81 (s, 1H), 7.1-7.4 (m, 3H), 7.30 (s, 1H), 7.74 (d. the Elements which is in the +2, +3 or +4 formal oxidation J-7.4 Hz, 2H). C{H} NMR (CD): 8 1.92, 429, State, 34.54, 54.68, 55.18, 55.31, 57.74, 58.66, 91.99, 101.95, 105.75, 122.80, 127.05, 127.37, 129.09, 130.30, 136.96, R independently each occurrence is hydrogen, R or 151.83, 153.52. TRP with the proviso that in at least two but not more than three occurrences R is TR is j is 1 or 2, and when j is 1, T is oxygen or Sulfur and when Polymerizations 25 j is 2, T is nitrogen or phosphorus, R’ independently each occurrence is a group having from 1 to 80 atoms not counting hydrogen, which is A two-liter Parr reactor was charged with 740 g of hydrocarbyl, hydrocarbylsilyl, halo-substituted Isopar-ETM mixed alkanes solvent (available from Exxon hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, Chemicals Inc.) and 118 g of 1-octene comonomer. Hydro 3O hydrocarby lamino-substituted hydrocarbyl, or gen was added as a molecular weight control agent by hydrocarbylsilyl-substituted hydrocarbyl, or two R' differential pressure expansion from a 75 mL addition tank groups are joined together forming a divalent ligand at 25 psi (2070 kPa). The reactor was heated to the poly grOup, merization temperature of 140 C. and saturated with eth 35 Z is a divalent moiety bound to the substituted indenyl ylene at 500 psig (3.4 MPa). The appropriate amount of group and bound to M by either covalent or coordinate catalyst and cocatalyst as 0.005M solutions in toluene were covalent bonds, comprising boron or a member of premixed in the drybox. After the desired premix time, the Group 14 of the Periodic Table of the Elements, and Solution was transferred to a catalyst addition tank and also comprising nitrogen, phosphorus, Sulfur or oxy injected into the reactor. The polymerization conditions 40 gen, were maintained for 15 minutes with ethylene on demand. The resulting Solution was removed from the reactor, and a X is an anionic or dianionic ligand group having up to 60 hindered phenol antioxidant (IrganoxTM 1010 from Ciba atoms including ligands that are cyclic, delocalized, Geigy Corporation) was added. Polymers formed were dried JU-bound ligand groups, in a vacuum oven set at 120° C. for about 20 hours. Results 45 X" independently each occurrence is a Lewis base ligand are in Table 1. having up to 20 atoms, p is a number from 0 to 5, when each X is an anionic TABLE 1. ligand, p is two less than the formal oxidation State of catalyst Density Mi Efficiency M, when Some or all X groups are dianionic ligand 50 groups each dianionic X group accounts for two Valen 1: A. O.895 5 1.3 2 B O.905 O.04 1.1 cies and p is correspondingly reduced in value; and 3 C O.914 O.04 1.O q is Zero, 1 or 2. 4 D 0.925 O.889 0.4 2. The metal complex of claim 1, corresponding to the *comparative, not an example of the invention 55 formula: A (N-(1,1-dimethylethyl)-1,1-dimethyl-1-(1,2,3,4,5-m)-2,3,4,5-tetramethyl II 2-4-cyclopentadien-1-ylsilanaminato(2-)-Ndimethyltitanium B N-(1,1-dimethylethyl)-1-((1,2,3,3a,7a-m)-5-methoxy-3-(1-pyrrolidinyl)- 1H-inden-1-yl)-1,1-dimethylsilanaminato(2-)-N)dimethyltitanium (Example 2 ach (1233,7-n-so-dimethoxy-3-(1-pyroidinyl)-1H-inden-1-yl)-N. 60 (1,1-dimethylethyl)-1,1-dimethylsilanaminato(2-)-N)dimethyltitanium (Example 8) D (N-(1,1-dimethylethyl)-1,1-dimethyl-5-((4a,5,6,7,7a-m)-6-methyl-5H indeno(5,6-d)-1,3-dioxol-5-yl)silanaminato(2-)-N)dimethyititanium (Example 10) 'melt index, determined by micromelt technique, dg/min 65 catalyst efficiency, g polymer?lug Ti US 6,555,634 B1 41 42 -continued -continued III VIII TRB.

1O IX IV

15 O

where Z, T, R, R, j, M, X, X", p and q are as previously defined with respect to formulas II, III IV and V. 25 4. The metal complex of claim 3 wherein where -Z is -(Z-Y), with Z* bonded to the cyclopentadienyl moiety and Y bonded to M, and

where T. R.j, M., Z, X, X", p and q are as previously defined in claim 1, and 35 R’ independently is hydrogen or a group having from 1 R* independently each occurrence is hydrogen, or a to 80 atoms not counting hydrogen, which is member selected from hydrocarbyl, hydrocarbyloxy, hydrocarbyl, hydrocarbylsilyl, halo-substituted Sillyl, halogenated alkyl, halogenated aryl, and combi hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, nations thereof, said R* having up to 20 nonhydrogen hydrocarby lamino-substituted hydrocarbyl, or 40 atoms, and optionally, two R* groups from Z, or an R* hydrocarbylsilyl-substituted hydrocarbyl, or two R' group from Z and an R* group from Y form a ring groups are joined together forming a divalent ligand System; grOup. p is 2, q is Zero, M is in the +3 or +4 formal oxidation 3. The metal complex of claim 2 corresponding to the State, and X is independently each occurrence chloride, formula: 45 methyl, benzyl, trimethylsilylmethyl, allyl, cyclopentadienyl, pyrollyl or two X groups together are VI 1,4-butane-diyl, 2-butene-1,4-diy1, 2,3-dimethyl-2- TRB. TRB. J bute ne-1,4-diyl, 2-methyl-2-butene-1,4-diyl, or J 50 Xylanediyl. RB' 5. The complex of claim 4 wherein Z* is SiR* and Y is -NR-. 6. The complex of claim 1 wherein M is titanium. 7. A catalyst composition for olefin polymerization com / Z. 55 X'qXpM prising in combination: VII (A) a catalyst component comprising a metal complex of TRP,B any one of claims 1-6 and (B) a cocatalyst component comprising an activating RB' 60 cocatalyst wherein the molar ratio of (A) to (B) is from 1:10,000 to 100:1. TRP,B 8. A proceSS for polymerizing olefins comprising contact ing one or more Co C-olefins under polymerization con / Z. ditions with a catalyst composition of claim 7. X'qXpM 65 k k k k k